Method for the control of undesirable vegetation



' addition compounds with nitrogenous bases.

United States Patent 3,235,357 METHOD FOR THE CONTROL OF UNDESIRABLE VEGETATION Harvey M. Loux, Hockessin, DeL, assignor to E. I. du Pont ale Nemours and Company, Wilmington, Del., a corporation of Delaware N0 Drawing. Filed Aug. 17, 1962, Ser. No. 217,521

19 Claims. (Cl. 71--2.5)

ingredient, at least one compound of the formula O O H II R-N R-N 1 e i X=\N Rg HX \N R;

where R is alkyl of 1 through 10 carbon atoms, substituted alkyl of 1 through 8 carbon atoms, aryl of through 10 carbon atoms, substituted phenyl, aralkyl of 5 through 13 carbon atoms, substituted aralkyl of 5 through 13 carbon atoms, alkenyl of 3 through 8 carbon atoms, alkynyl of 3 through 8 carbon atoms, cycloalkyl of 3 through 12 carbon atoms, cycloalkenyl of 4 through 12 carbon atoms, cycloalkyl alkyl of 4 through 13 carbon atoms, cycloalkenyl alkyl of 5 through 13 carbon atoms, (substituted cycloalkyl)alkyl of 5 through 14 carbon atoms, (substituted cycl'oalkenyDalkyl of 5 through 14 carbon atoms, and cyano;

R is chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, nitro, alkoxymethyl of 2 through 6 carbon atoms, hydroxy alkyl of 1 through 6 carbon atoms, alkenyl of 3 through 6 carbon atoms, thiocyanato, cyano, thiolmethyl, alkylthio containing 1 through 4 carbon atoms, bromomethyl, methylthiomethyl, fluoromethyl, chloromethyl, phenylthiomethyl or carboxymethylthiomethyl;

R is chloro, brorno, alkyl of 1 through 5 carbon atoms, chloroalkyl of 1 through 4 carbon atoms, bromoalkyl of 1 through 4 carbon atoms, or alkoxy of 1 through 5 carbon atoms; and

X is oxygen or sulfur.

The salts of these compounds can also be used according to this invention. By salts is meant those compounds formed with such cations as sodium, potassium, lithium, calcium, magnesium, barium, strontium, iron, manganese and quaternary ammonium.

Some of the uracils of Formula 1 also form novel 1:1 The exact structure of these compounds is not known. Although the compounds are, generally speaking, poorly soluble 3,235,357 Patented Feb. '15, 1966 ice in water, they are, according to the best available information, believed to be essentially salt-like in structure. They Will be symbolized by the following formula, with the understanding that it is representative only, and is not intended to illustrate actual structure:

where R and R are defined as in Formula 1, and NB is a nitrogenous base having an ionization constant K of IO- in water.

Suitable nitrogenous bases are substituted, unsubstituted, cyclic and acyclic Amines Amidines, and Guanidines.

The amines can be primary, secondary or tertiary amines, polyammes, .arylamines, or heterocyclicarnines. Illustrative of such amines are:

Sec-butylamine 2-amino-2-methyl-1,3-propanedio1 Trimethylenediamine Ethanolamine Dodecylamine Ethylenediamine HexamethyIenediamine Cocoadiamine Tallowdiamine Hexamethyleneimine Cyclohexylamine Methoxypropylamine Methylamine Dimethylamine Trimethylamine Ammonia Ethylamine Propylamine Butylamine Octylamine Pyridine Piperidine Tetramethylguanidine Acetamidine Benzylamine Diethylenediamine 2-aminobutanol-1 Z-aminooctanol-l Within the scope of Formula 1 is a group of novel compounds. These compounds are those of the formula (3) 0 o X i X ll Y C N Halogon Y: C N Hal0ge11 Z 0: OI-I (i) hero- J-om N/ \N where:

X is methyl or ethyl,

Y is hydrogen or methyl, and

Z is an alkyl group of 1 through 6 carbon atoms, and the salts of these compounds, as defined for Formula 1.

Certain 3,5,6-substituted uracils of Formula 1 also form water stable, novel complexes With phenol and substituted phenols. These complexes have the formula R and R are as defined in Formula 1,

X is hydrogen, chlorine, nitro, alkyl of 1 through 3 carbon atoms, bromine or -OR R is alkyl of 1 through 3 carbon atoms,

Y is chlorine or alkyl of 1 through 3 carbon atoms,

In is a number 1 through 5, and

n is 1 or 2.

These complexes are also herbicidal, and in this respect, have some advantages over the uracils per se, viz., higher solubility in oils and solvents. They are formulated into herbicidal compositions in the same Way as are the uracils themselves.

Preferred for use according to this invention because they are etfective as herbicides at lower rates of application are compounds of the formula N/ CH;

Where:

R is alkyl of 2 through 8 carbon atoms, substituted alkyl of 2 through 8 carbon atoms, phenyl, substituted phenyl, aralkyl of through 10 carbon atoms, substituted aralkyl of 5 through 10 carbon atoms, cycloalkyl of 3 through 12 carbon atoms, cycloalkenyl of 5 through 12 carbon atoms, cycloalkyl alkyl of 4 through 13 carbon atoms, and (substituted cycloalkyl) alkyl of 5 through 14 carbon atoms; and

R is chlorine, bromine, iodine, methyl, hydroxymethyl,

methoxymethyl and nitro.

Especially preferred for use because of their herbicidal effectiveness are:

3- l-lower alkylethyl -5-halogeno-6-methyluracils,

3- (2-lower alkylethyl -5-ha.logeno-6-methyluracils,

3-( l-lower alkylisopropyl -5-halogeno-6-methyluracils, 3- cycloalkyl) -S-halogeno-6-methyluracils,

3- (cycloalkenyl -5-halogeno-6-methyluracils,

3 (phenyl) -5 halogeno--methyluracils,

3- (bicycloalkyl -5-halogeno-6-methyluracils,

3- bicycloalkenyl -S-halogeno-6-methyluracils,

3- (tricycloalkyl -5-halogeno-6-methyluracils, and

3 tricyclo alkenyl -5-halogeno-6-methyluracils.

In the foregoing list, lower alkyl means an alkyl radical containing 1 through 4 carbon atoms.

In Formulae 1, 2, 4 and 5 the term substituted alkyl is intended to include such radicals as Bromoalkyl of 1 through 8 carbon atoms,

Chloroalkyl of 1 through 8 carbon atoms, Hydroxyalkyl of 1 through 8 carbon atoms, Alkoxyal-kyl of 2 through 8 carbon atoms,

Alkoxy carbonyl alkyl of 3 through 8 carbon atoms, and Cyanoalkyl of 2 through 8 carbon atoms.

4 Similarly, the terms ary and substituted phenyl embrace radicals such as Phenyl,

Naphthyl,

O-biphenyl,

Pyridyl,

Chlorophenyl,

Bromophenyl,

Alkoxyphenyl,

Dibromophenyl,

Fluorophenyl,

Trichlorophenyl,

Alkylphenyl of 7 through 11 carbon atoms, Dialkylphenyl of 8 through 12 carbon atoms, Chloroalkylphenyl of 7 through 10 carbon atoms, Nitrochlorophenyl,

Nitrophenyl,

Dichloronitrophenyl,

Chloroa'lkoxyphenyl of 7 through 11 carbon atoms, Trifluoromethylphenyl,

Tetrahydronaphthyl, and

Indenyl.

The terms aralky and substituted aralky are intended to include such radicals as Furfuryl,

Benzyl,

Phenylal-kyl of 8 through 11 carbon atoms (total),

Ohlorobenzyl,

Dich lorobenzyl,

Alkylbenzyl of 8 through 11 carbon atoms (total),

Dialkyl'benzyl of 9 through 13 carbon atoms (total),

Nitrobenzyl,

Alkoxybenzyl of 8 through 11 carbon atoms (total),

and

Naphthylmethyl.

The terms cycloalkyl, cycloalkenyl, cycloalkyl alkyl, and cycloalkenyl alkyl will include Cyclohexyl,

Cyclohexenyl,

Cyclohexylalkyl, Cyclohexenylalkyl, Cyclopentyl,

Cyclopentenyl, Cyclopentylalkyl, Cyclopentenylalkyl,

Norbornyl, n Norbornenyl,

Norbornylalkyl, Norbornenylalkyl, Bicyclo(2,2,2)octyl,

Bicyclo (2,2,2) octenyl,

Bicyclo( 2,2,2 octylalkyl, Bicyclo(2,2,2)octenylalkyl, Cyclopropyl,

Cyclobutyl,

Cyclobutylalkyl,

Cyclobutenyl, Cyclobutenylalkyl, Hexahydroindanyl, Tetrahydroindanyl, Hexahydroindenyl, Hexahydroindenyl alkyl, Tetrahydroindanyl alkyl, Hexahydroindanyl alkyl, Hexahydro-4,7-methanoindenyl, Tetrahydro-4,7-methanoindanyl, Hexahydro-4,7-methanoindanyl, I-IeXahydro-4,7-methanoindenyl alkyl, Tetrahydro-4,7-methanoindanyl alkyl, Hexohydro-4,7-methanoindanyl alkyl, Decahydronaphthyl, Decahydronaphthyl alkyl, Tetrahydronaphthyl,

These cyclic substituents can be further substituted with alkyl groups 1 through 4 carbon atoms, methoxy, chlorine and bromine.

In the process of combining the various 3,5,6-substituents described above for R, R and R it is surprising to find that strikingly similar herbicidal activity can be obtained with seemingly unrelated substituents. On the other hand, it is equally surprising to find useful selective phytotoxicity (applicable in certain crop areas) when a relatively minor structural modification for R (for example a normal alkyl chain altered to a branched chain) is made. Each S-Substituent (described for R above) for example, has a maximum and minimum range of herbicidal effectiveness and/or specie selectivity dependent on the nature of the substituent in the 3- or 6-position. There is little continuity of herbicidal effect which can be ascribed to a particular substituent independently of the other two substituents in the 3,5,6-positions.

UTILITY These uracils represent a new class of herbicides offering farmers and property owners a new and effective method for the control of undesirable vegetation. These compounds are unique in that they exert their action against both broadleaf and grass weeds, are effective against hard to-kill nutsedge and perennial grasses such as quack grass, Johnson grass, and Bermuda grass, and are effective on highly adsorptive substrates such as railroad ballast, heavy clay soil, and soils high in organic matter.

This combination of properties makes these compounds useful wherever general weed control is required, such as industrial areas, railroad rights-of way, and areas adjacent to croplands in agricultural areas.

Certain of the uracils also exhibit selective herbicidal action in crops. By properly selecting a uracil of the invention and a rate and time of application, annual grass and broadleaf seedlings in such crops as asparagus, corn, flax, sugar cane, pineapple, safllower, peanuts, citrus, alfalfa, strawberries, gladiolus, stone fruits and cucurbits can be controlled.

By proper selection of rate and time of application, certain of the uracils can also be used to control weeds growing in dormant crops.

This selective activity and activity on weeds growing in dormant crops is described in more detail in the examples.

The precise amounts of uracils to be used in any given situation will, of course, vary according to the particular end result desired, the use involved, the plant and soil involved, the formulation used, the mode of application, prevailing weather conditions, foliage density and like factors. Since so many variables play a role, it is not possible to indicate a rate of application suitable for all situations. Broadly speaking, the compounds are used at levels of about pound per acre to about 25 pounds per acre. For selective weed control in crops, rates of A to 8 pounds per acre will generally be used. More of the active material can be used to control difficult-to-kill species growing under adverse conditions. Economic factors, such as inaccessibility of the area to be treated, e.g., fire breaks in forests, may also favor higher rates, with less frequent treatments.

6 PREPARATION OF THE COMPOUNDS Those uracils of Formula 1 where R is alkyl, or alkenyl, as well as the uracil starting reactants for the reactions of Equations 11 to 15, can be prepared by methods heretofore described in the literature. For example, one method for the preparation of these compounds is illustrated by the following equations:

For more general details, note the publication by Behrend and Myer in Ann., 314, 219 (1901), and also Ber., 33, 622 (1900).

In the method of Equations 6 and 7, the esters of ,s-amino-uJii-unsaturated acids are first prepared by reacting the corresponding ,B-keto esters with aqueous ammonia [Conrad and Epstein, Ber., 20, 3054 (1887)]. These properly substituted B-amino-a,B-unsaturated esters are then reacted with an isocyanate or isothiocyanate in an inert solvent such as toluene or xylene, and heated for a short interval of time at reflux temperature.

The reaction mixture is chilled, filtered, and the filtrate distilled to remove the solvent. Generally, a viscous liquid residue remains which is crude 3-(3substitutedureido)-a,B-unsaturated ester. This can be reacted without further purification with an aqueous alcoholic alkaline solution at reflux temperature to bring about the desired uracil ring closure. At this point, the reaction is made slightly acidic with a strong acid such as hydrochloric acid and distilled to remove the alcohol. After the remaining aqueous solution has been chilled, the corresponding substituted uracil separates as an essentially pure solid.

Another method for preparing the uracil starting reactants is illustrated by the following equations:

0 O benzene [L H acid catalyst LNH CH C-CH COOC Eh A -I'Iz0 According to Equations 8 and 9, an appropriately substituted urea or thiourea is reacted with a fi-keto ester or an zit-substituted fi-keto ester substituted with such radicals as alkoxy, fluorine, alkyl, or alkenyl, and an acid catalyst, at reflux in a solvent from which water is removed continuously. After the water has all been removed, the solution is stripped and taken up in ethanol containing a base such as sodium methoxide. After a few minutes reflux, the solvent is removed, and the residual oil taken up in water and acidified, whereupon the desired product separates in crystalline form.

The product formed at the end of the first step, i.e., after the water has been removed, is a ureido compound of the type referred to in Equation 8. It can be isolated and purified if desired; however, this is not necessary or advantageous.

These ureido compounds referred to above are believed to exist in either or both of two tautomeric forms, as illustrated in the following equation:

3 NH s NH 3-substituted-6-methyluracil starting reactants can also be formed by the interaction of alkylurethans and N-substituted acetoacetamides in the presence of alkoxide.

The uracils which are substituted in the 5-position with halogen, nitro, thiocyanato, chloromethyl and hydroxymethyl groups can be prepared by methods heretofore described in the literature for related compounds.

For example, the preparation of those compounds having a halogen substituent in the 5-position is illustrated by Equation 11. For more general details, see I. Am. Chem. Soc. 61, 1015 (1939); Ann., 305, 314; Ann., 352, 242; and Ann., 441, 192.

The S-nitro uracils are prepared by direct nitration of uracils having no substituent in the 5-position, as illustrated in Equation 13. For a description of this method, see J. Am. Chem. Soc., 30, -1 156 (1908).

The S-thiocyano uracils are prepared by direct thiocyanogenation as illustrated by Equation 14. For more details concerning this procedure, see I. Am. Chem. Soc.,

63, 2323 (1941); Org. Syntheses, Coll. Vol. II, 574 (1943); and Helv. Chim. Acta, 19, 1411 (1936).

The reaction of formaldehyde with uracils not substituted in the 5-position gives uracils substituted in the 5- position with a hydroxymethyl group, as illustrated by Equation 15. For greater detail see Gazz. Chim. Ital., 79, 447 (1949).

These S-hydroxymethyl uracils can be easily reacted with alcohols, methylmercaptan, thiophenols, thionylchloride, or mercaptoacetic acid to give corresponding 5- alkoxymethyl, -methylthiomethyl, -phenylthiomethyl, -chloromethyl, and carboxyrnethylthiomethyl uracils.

6-chlorouracil, prepared by acidic hydrolysis of 2,4- dimethoxy-6-chloropyrimidine (see British Patent 677,- 342), can serve as an intermediate for the preparation of many uracils. The following diagram illustrates this:

Methods for carrying out the reactions illustrated in the foregoing diagram are well described in pyrimidine literature. These reactions, as well as many related ones, will be easily carried out by those skilled in this field of chemistry.

The salts of the compounds of Formula 1 are prepared by conventional methods such as dissolving the free uracil in an aqueous or nonaqueous solution of at least an equimolar amount of a base or basic salt containing the desired cation. For example, a sodium salt can be prepared by dissolving the uracil in water containing an equimolar amount of sodium hydroxide. The salt can then be isolated from the solution by removal of the water. The uracil salts which are not soluble in water can be prepared by treating an aqueous solution of an alkali metal salt of the uracil with an aqueous solution of a water-soluble salt of the metal.

The quaternary ammonium salts of the compounds of Formula 1 are prepared by reacting the substituted uracil with an appropriate quaternary ammonium hydroxide. Since these hydroxides are generally available in solution,

9 the reaction is most conveniently carried out in the same solvent. If the solvent-free salt is desired, it can be easily prepared by removing the solvent.

Alternatively, the quaternary ammonium salts of the uracils can be prepared in a dry inert solvent such as toluene or xylene. The appropriate quaternary ammonium halide is then added with stirring and, if necessary, mild heating. The sodium halide which forms is removed by filtration, leaving the quaternary ammonium salt of the uracil in solution. If desired, the solvent-free salt can be prepared by removing the solvent, preferably in vacuo.

The nitrogenous base-addition compounds of Formula 2 are prepared by mixing together equimolar quantities of an appropriate uracil and a nitrogenous base. The mixture is gradually heated, with stirring, until a clear melt is formed. On cooling, the addition compound crystallizes. This product can then be recrystallized from a solvent such as benzene, cyclohexane, nitromethane or acetonitrile.

It is sometimes advantageous to use an inert solvent medium to carry out the reaction. Such a solvent moderates the reaction by acting as a heat sink, and allows better control of the reaction, especially if it is being carried out on a large scale. Suitable inert solvents are benzene, cyclohexane, nitromethane, acetonitrile and dioxane.

When an inert solvent is used, the addition compounds are prepared by dissolving the amine in the solvent and then adding the uracil gradually, with stirring. Stirring is continued for from ten minutes to two hours. Mild heating may be necessary. Some addition compounds precipitate and can be removed by filtration. Other addition compounds are isolated by evaporating the solvent. The addition compounds prepared in this way are suitable for use without further purification, but can be purified by recrystallization if desired.

In some instances, the uracil and amine are highly soluble in the inert solvent, but the addition compound is not, and so it can be filtered 01f pure when the reaction is complete.

The complexes of Formula 4 are formed by co-melting the uracil and phenol in a 1:1 to 2:1 (uracilzphenol) ratio. They can also be formed by codissolving the reactants, in the same ratio, in a nonpolar solvent such as nitromethane or a mixture of nitromethane and cyclohexane. Process conditions and isolation procedures are the same as those described above for the addition compounds.

HERBICIDAL COMPOSITIONS The uracil compounds in Formulae 1 through 5 can be prepared for use by incorporating them with adjuvants.

The amount of herbicide in such preparations can vary over a wide range according to need. Generally speaking, they will contain from about 0.5 to 95%, by weight of a uracil.

Powder and dust preparations can be made by mixing uracils of the invention with finely-divided solids such as tales, natural clays, pyrophyllite, diatomeous earth; flours such as walnut shell, wheat, redwood, soya bean and cot ton seed; or inorganic substances such as magnesium carbonate, calcium carbonate, calcium phosphate, sulfur and lime. These preparations are made by thoroughly blending the active ingredient and the solid. The particles in such preparations are preferably less than 50 microns in average diameter.

Water-soluble preparations can be prepared by mixing a uracil with an alkaline solubilizing agent. Solid bases having a pH of at least 9.5 in a 1% aqueous solution, such as sodium or potassium phosphates, silicates, carbonates, borates, oxides or hydroxides, are suitable. The preparations can contain from 0.5 to 80% active ingredient and from 5 to 99.5% of the solubilizing agent.

Granules and pellets can be made by mixing a finely- 10 divided uracil with a suitable clay, moistening this mixture with from 15 to 20% by weight of water, and then extruding the mass through a suitable die under pressure. The extrusions are cut into pre-determined lengths and then dried. These pellets can be granulated if desired.

Granules or pellets can also be prepared by spraying a suspension or solution of a uracil onto the surface of a preformed granule of clay, vermiculite or other suitable granular material. If the uracil is in solution, it will penetrate into the pores of the granule and so will adhere without the aid of a binding agent. When the active material is insoluble in the liquid and is carried as a suspension, it is preferable that a binding agent such as goulac, dextrin, swollen starch, glue or polyvinyl alcohol be added. In either case, the granule is then dried and ready for use.

The uracils can also be prepared in non-aqueous liquids. Aliphatic and aromatic hydrocarbons, especially those derived from petroleum and having boiling points of from C. to 400 C. are preferred. Hydrocarbons having lower boiling points should not be used because of their undesirable volatilization characteristics and inflammability. These liquid preparations are made by milling the components in a mill such as a pebble mill until the particles have average diameters of from 1 to 50 microns, preferably 5 to 20 microns.

The herbicidal preparations, whatever physical form they take, can also contain a surface-active agent. The surfactant renders the preparations readily dispersible in l quids and improves their action on waxy leaves and the like. For general application, surface-active agents are used in the preparations at concentrations of from about 1 to 10%, by weight. Levels of from 0.5 to 6 parts of surfactant for each part of uracil, however, give unusual and unexpected results. Preparations having these higher levels of surfactants show greater herbicidal effectiveness than can be expected from a consideration of activity of the components used separately.

The term surfaceactive agent is intended to include wetting agents, dispersing agents, suspending agents and emulsifying agents. Surface-active agents suitable for use are set forth in Detergents and Emulsifiers upto-date, 1962, John W. McCutcheon, Inc, Morristown, New Jersey. Other surface-active agents which can be used in these preparations are listed in US. Patents 2,139,276; 2,412,510; 2,426,4 17; 2,655,447; and Bulletin E-607 of the Bureau of Entomology and Plant Quarantine of the US. Department of Agriculture.

The preparations can also optionally contain adhesives such as gelatin, blood albumin and such resins as rosin alkyd resins. These increase retention and tenacity of deposits following application.

The salts of the compounds of Formula 1 are especially advantageous for use as herbicides because they are soluble in water and can be applied as aqueous solutions.

With respect to the nitrogenous base-addition compounds of Formula 2, it has been found that preparation with polar low-molecular weight amines, such as ethanolamines, propanolamines and butanolamines gives addition compounds soluble in water, especially when the amine is present in excess. Other amines, such as piperidine and octanolamines give addition compounds which are soluble in both Water (with an excess of amine present) and hydrocarbon solvents. At the other end of the scale, amines such as dodecylamines, cocoaamines and tallowamines give the addition compounds high hydrocarbon solubility.

Thus, it is apparent that by properly selecting an amine and forming an addition compound with it, uracils of Formula 2 can be formulated as aqueous solutions, wettabl-e powders, or as an oil-emulsifiable or oil-extendable formulation. In this way, the nitrogenous base-addition compounds give formulation and application advantages, While still maintaining the desirable herbicidal characteristics of the parent uracils.

11 FORMULATION WITH OTHER HERBICIDES The herbicidal compositions of this invention can be formulated to contain two or more of the uracils. They can also be formulated to contain other known herbicides in addition to the uracils to give compositions which have advantages over the individual components.

Among the known herbicides which can be combined with the uracils of Formula 1 are:

SUBSTITUTED UREAS 3- 3 ,4-dichlorophenyl) -1,1-dimethylurea 3-(4-=chlorophenyl)-1,1-dimethylurea 3 -phenyl-1, 1-dimethylurea 3-(3,4-dichlorophenyl) -3-methoxy-1, l-dimethylurea 3-(4-chlorophenyl) -3-methoxy-1, l-dimethylurea 3- 3 ,4-dichlorophenyl) -1-n-bu.tyl-1-methylurea 3- 3 ,4-dichlorophenyl) -1-methoxy-1-methylurea 3- (4-chlorophenyl) -1-methoxy 1-methylurea 3-(3,4-dichlorophenyl)-1,1,3-trimethylurea 3- 3,4-dichlorophenyl) 1 1 -dietl1ylurea 3- (p-chlorophenoxyphenyl) -1,1-dimethylurea These ureas can be mixed with the uracils of this invention in proportions of form 1:4 to 4:1, respectively, the preferred ratio being 1:2 to 2: 1.

SUBSTITUTED TRIAZINES These triazines can be mixed with the uracils of this invention in proportions of from 1:4 to 4: 1, respectively, the preferred ratio being 112 to 2: 1.

PHENOLS Dinitro-o-sec.-butylphenol and is salts Pentachlorophenol and its salts These phenols can be mixed with the uracils of this invention in the proportions of 1: 10 to 20: 1, respectively, the preferred ratio being 1:5 to 5: 1.

CARBOXYLIC ACIDS AND DERIVATIVES The following carboxylic acids and derivatives can be mixed with the uracils of this invention in the listed proportions:

A. 2,3,6-trichlorobenzoic acid and its salts 2,3,5,6-tetrachlorobenzoic acid and its salts 2-methoxy-3,5,6-trichlorobenzoic acid and its salts 2-meth'oxy-3,6-dichlorobenzoic acid and its salts 3-amino-2,5-dichlorobenzoic acid and its salts 3-nitro-2,5-dichlorobenzoic acid and its salts 2-methyl-3,6-dichlorobenzoic acid and its salts 2,4-dichlorophenoxyacetic acid and its salts and esters 2,4,S-trichlorophenoxyacetic acid and its salts and esters (2-methyl-4-chlorophenoxy)acetic acid and its salts and esters 2-(2,4,5-trichlorophenoxy)propionic acid and its salts and esters 2-(2,4,5-trichlorophenoxy)ethyl-2,2-dichloro-propionate 4-(2,4-dichlorophenoxy)butyric acid and its salts and esters 4-(2-methyl-4-chlorophenoxy)butyric acid and its salts and esters 2,3,6-trichlorobenzyloxypropanol Mixed in a 1:16 to 8:1 ratio, preferably a 1:4 to 4:1 ratio.

B. 2,6-dichlorobenzonitri1e Mixed in a 1:4 to 4:1 ratio, preferably a 1:3 to 3:1 ratio.

C. Trichloroacetic acid and its salts Mixed in a 1:2 to 25:1 ratio, preferably a 1:1 to 8:1 ratio.

D. 2,2-dichloropropionic acid and its salts Mixed in a 1:4 to 8:1 ratio, preferably a 1:2 to 4:1 ratio.

E. N,N-di(n-propy1)thiolcarbamic acid, ethyl ester N,N-di(n-propyl)thiolcarbamic acid, n-propyl ester N-ethyl-N-(n-bu=tyl)thiolcarba rnic acid, ethyl ester N-ethyl-N-(n-butyl)thiolcarbamic acid, n-propyl ester Mixed in a 1:2 to 24:1 ratio, preferably a 1:1 to 12:1 ratio.

F. N-phenylcarbamic acid, isopropyl ester N-(m-chlorophenyl)carbamic acid, isopropyl ester N-(m-chlorophenyl)carbamic acid, 4-chloro-2-butynyl ester Mixed in a 1:2 to 24:1 ratio, preferably a 1:1 to 12:1 ratio.

G. 2,3,6-trichlorophenylacetic acid and its salts Mixed in a 1:12 to 8:1 ratio, preferably a 1:4 to 4:1 ratio.

H. 2-chloro-N-N-diallylacetamide Maleic hydrazide Mixed in a 1:2 to 10:1 ratio, preferably a 1:1 to 5:1 ratio.

INORGANIC AND MIXED INORGANIC-ORGANIC SALTS The following salts can be mixed With the uracils in the listed proportions:

A. Calcium propylarsonate Disodium monomethylarsonate Octyl-dodecylammoniummethylarsonate Dimethylarsinic acid Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1 ratio.

B. Sodium arsenite Mixed in a 1:5 to 40:1 ratio, preferably a 1:4 to 25:1 ratio.

C. Lead arsenate Calcium arsenate Mixed in a 150:1 to 600:1 ratio, preferably a :1 to 400:1 ratio.

D. Sodium tetraborate hydrated, granulated Sodium metaborate Sodium pentaborate Polyborchlorate Unrefined borate ore such as borascu Mixed in a 3:1 to 1500:1 ratio, preferably in a 6:1 to 1000:1 ratio.

13 14 E. Ammonium thiocyanate 3-isopropyl-S-bromouracil 3-sec.-butyl-5-bromouracil 7 ratlggixed in a 1.10 to .0.1 ratio, preferably a 1.5 to 5.1 3 Sec. buty1 s chlowuracil F Sodium chlorate ratlivixed in a 1:6 to 6:1 ratio, preferably a 1:2 to 2:1

Mixed in a 1:1 to 40:1 ratio, preferably a 2:1 to 20:1 ratiu D. 3-isopropyl-1-trichloromethylthio-5-bromo-6-methyl- G A If uracil mmomum amate '3-cyclohexyl-1-trichloromethylthio-S-bromo-6-methyl- Mixed in a 1:1 to 100:1 ratio, preferably a 1:1 to 50:1 uracil ratio. 3-sec.-butyl-1-acety1-5-bromo-6-methyluracil OTHER ORGANIC HERBICIDES 3-isopropyl-1-acetyl-5-bromo-6-methyluracil 3-1sopropyl-1-trichloromethylth1o-5-chloro-6-methyl- These organic herbicides can be mixed with the uracils in the listed proportions: 5,6 dihydro (4A,6A) dipyrido (1,2 A2',1' c)pymZin Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1

ium dibromide ratio Mixed in a 1:20 to 16:1 ratio, preferably a 1:5 to 5:1 Ofthe foregomg are Welghtranos' EXAMPLES uracil B. 3-amino-1,2,4-triazole Mixed in a 1:20 to 20:1 ratio preferably a 1:5 to 5:1 In order that the invention may be better understood,

the following examples are given:

ratio.

C. 3,6-endoxohexahydrophthalic acid PREPARATION OF ACTIVE INGREDIENTS Mixed ina 1:3 to 20:1 ratio, preferably a 1:2 to 10:1 Example 1 Preparmi0n of ratio.

6-methyluracil D. Hexachloroacetone Eight parts of chlorine are added to a stirred solution of Mixed in a 1:2 to 16:1 ratio preferably a 1:1 to 8:1 18.2 parts of 3-butyl-6-methyluracil in 100 parts of glacial ratio acetic acid. The temperature is maintained below 30 C. E. Diphenylacetonitrile during this addition. The solution is stirred /2 hour N,N-dimethyl-a,a-diphenylacetamide longer at room temperature, then poured into ice water,

N,N-di-n-propyl-2,6-dinitro-4-trifluoromethylaniline r whereupon a solid separates. This solid is collected by N,N-di-n-propyl-2,6-dinitro-4-methylaniline filtration and washed well with Water to give 21 parts of crude 3-butyl-5-chloro-6-methyluracil, melting at 120- Mixed a 1'10 to 30.1 preferably a to 201 150 C. It is then recrystallized from a mixture of ratio.

cyclohexane and ethyl acetate to give 7.5 parts of pure P y y P PY P P 3-butyl-S-chloro-6-methyluracil, melting at 163164 C.

amidothiate 2,3,5,6-tetrachloroterephthalic acid, dimethyl ester Example 2.Preparati0n 0f 5-br0m0-3-butyl- Mixed in a 1:4 to 20:1 ratio, preferably a 1:3 to 15:1 6'methylu'acll ratio.

Seventeen parts of bromine are added over a 20-minute G. 2,4-dichloro-4-nitr-odiphenyl ether period to a stirred solution of 18.2 parts of 3-butyl-6- inethyluracil in 100 ml. of glacial acetic acid. The tem- Mlxed m a to 301 ratlo preferably a to perature is maintained below 30 C. during this addition.

ratio. The solutlon 1s stirred at room temperature for an addi- OTHER SUBSTITUTED URACILS tional 1 /2 hours, then poured into a mixture of ice and These uracils can be mixed with other substituted water, with stirring. The White solid which separates is uracils, in the proportions listed below. Methods for the collected by filtration, washed well with water, and dried preparation of the listed uracils can be found in copending in a vacuum oven. Thirty-five parts of essentially pure applications Serial Nos. 167,434, filed February 1, 1962; S-bromo-3-butyl-6-methyluracil are obtained. The com- 89,672, filed February 16, 1961; 89,673, filed February 16, pound can be purified by recrystallization from a mixture 1961; and 89,674, filed February '16, 1961. of hexane and ethyl acetate to give 17.5 parts of pure material, appearing as white needles and melting at A. 3-cycl-ohexyl-6-methylurac1l 158-1600 C.

3-cyclohexyl-6-ethyluracil 3-cyclohexyl-6-sec.-butyluracil 3-cyelopentyl-6-methyluracil 6'methylm 3'cydohexyl'6'lsopropylumcll Seventeen parts of bromine are added over a 20-minute Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1 period to a stirred solution of 20.8 parts of 3-cyclohexy1- ratio. 6-methyluracil in 100 parts of glacial acetic acid. The

5 temperature is maintained below 30 C. during the addi- 3-cyclohexyl-5,6-tlmethyleneum?ll tion. The solution is stirred at 20-30 c. for an addi- 3e"buty1'si6'trfmethyleneuracfl tional 1 /2 hours, and is then poured, with stirring, into 2 3'lsopropyl'st6'mmethyleneuracll volumes of ice water, whereupon a white solid separates. 3lsopropyl'56'tcn'amethylensuracll This solid is collected by filtration, washed well with water, 3-1sopropyl-5,6-pentamethyleneuracll and dried in a vacuum to give essentially pure 3-cyclohexyl-S-bromo-6-methyluracil. It can be recrystallized from ethanol if desired. The melting point of the material is 243244 C.

C. 3-cyclohexyl-S-bromouracil The following compounds are prepared as in Examples 3-cyclohexyl-S-chlorouracil 1, 2 and 3 by substituting the listed amounts of the sub- Mixed in a 1:6 to 6:1 ratio, preferably a 1:4 to 4:1 ratio.

19 by filtration. The solid is extracted with 200 .parts by weight of a 1 N sodium hydroxide solution. Acidification of the basic filtrate gives essentially pure solid 3-phenyl- 5-bromo-6-methyl2-thiouracil, melting at 230-232 C.

Example 7.Preparatin of -z'0d0-3-isopr0pylo-methyluracil A mixture of 168 parts by weight of 3-isopropyl-6- methyluracil, 1000 parts by weight of acetic acid, and 253 parts by weight of iodine is stirred at 100 C. as 75 parts by weight of fuming nitric acid are gradually added. When the addition is complete, the dark colored solution is refluxed for about one-half hour and then cooled to ice-bath temperature.

Excess iodine which precipitates is filtered off and the filtrate is diluted with 4000 parts by weight of cold water. The iodine remaining in solution is reduced to iodide ion by adding a saturated solution of sodium bisulfite until the solution becomes colorless.

The aqueous solution is extracted with 6000 parts by weight of methylene chloride. The organic layer is separated, washed with saturated sodium bicarbonate solution, and then dried with 200 parts by weight of magnesium sulfate.

The 5-iodo-3-isopropyl-6-methyluracil is recrystallized from acetonitrile. It melts at 181 C.

Example 8.Preparation of 3-butyl-6-metkyl-5- nitrouracil A solution of 40 parts by volume of fuming nitric acid and 40 parts by volume of fuming sulfuric acid (20% S0 is stirred at 25-30" C. while 20 parts by weight of 3-butyl-6-methyluracil are added portion-wise over a 30- minute period. The solution is stirred an additional 30 minutes, then poured slowly into 4 volumes of a stirred ice-water mixture. The uracil separates out as a pale yellow solid. It is collected by filtration, washed well with water, and air-dried. One recrystallization from 1,1,1- trichloroethane gives ananlytically pure 3-butyl-6-methyl- S-nitrouracil, melting at 170-171 C.

Example 9 The following S-nitro substituted uracils can be prepared in a manner similar to Example 8 above by substituting equivalent amounts of the substituted uracil starting reactants set forth in the following table for the 3- butyl-6-methyluracil shown in Example 8:

Uracil starting reactant fi-nltrouraoll product 3-(3a,4,5,G,7,7a-hcxahydro-4,7-

ruethano-5-indenyl)-6-methyluracil.

3-cyclohcxyl-6-chlorouracil 3-(3-methoxypropyl)-6-methyluracil.

3-tcrt.-butyl-6-methy1uracil 3-(o-ruothoxycyclohcxyl)-6-methyluracil. 3-beuzyl6 mothy1-2thiouracil 3-dccyl-6-butyluracil 3-cyclohexyl-6-methyluracil 3-cyclopenteuyl-6-butyl-2-thiouracil.

3isopropyl-fi-methyluracil 3 sec. -butyl-6-mcthyluracil 3-cyclohexyl-6-ethyluraci1 B-phenyl-G-methyluracil Example 10.Preparation of 3-butyl-5,6-dimethyluracil A mixture of 23.2 parts by weight of butylurea 28.8 parts by weight of ethyl 2-methyl-3-ketobutyrate, 0.5 part by weight of orthophosphoric acid, and 200 parts by weight of benzene was heated at reflux. Water was collected in a Dean-Stark trap. After 24 hours, 2.5 parts by weight of water had been collected and there appeared to be no more separatin The solution was decanted and evaporated to a mixture of viscous oil and solid, which was taken up in 200 parts by weight of ethanol containing 10.6 parts by weight of sodium methoxide and heated at reflux for 10 minutes. Most of the ethanol was re-' moved under reduced pressure and the residue was taken up in just sufiicient water to dissolve it. Concentrated hydrochloric acid was added to lower the pH to 4 and the resulting white solid was collected by filtration. This was recrystallized from an ethanol-water mixture to give pure 3-butyl-5,6-dimethyluracil, melting at 1l6.5-l17 C.

The following uracils are similarly prepared by substituting equivalent amounts of the ureas and thioureas and equivalent amounts of the fi-keto esters set forth in the table for the butylurea and ethyl 2-methyl-3-ketobutyrate:

B-Keto ester Parts by Urea Parts by Uracil product weight weight Ethyl 2-mcthyl-3-ketobutyratc 28. 8 Sec.-amylurea 26. 0 3-sec.-amyl-5,6-dimethyluracil. Do 28. 8 lsopropylurea 21. 0 3'isopropyl-fifidunethyluracll. Ethyl 2-buty1-3'ketovalerate 39. 8 Amylurea 26.0 3-am yl-S-butyl-6-ethylurac1l. Ethyl 2-ethyl-3-ketovalcrate. 34. 2 Propylthiourca. 23. 6 3-pr0pyl-5,6-d1ethyl-2-thiouracil. Ethyl 2-methyl-3-ketobutyrate 28. 8 Sec-butylurea. 23. 5 3-sec.-butyl;5,6-dnnethyluracl1.

Do 28. 8 Allylurea 20. 0 3-allyl-5,fi-dimcthyluracil. Ethyl 2-methyl-3-ketoheptanoate 37. 0 Propynylurea 19. 6 3-propynyl-fi-rnethyl-fi-butyluracil. Ethyl 2-methyl-3-ketobutyrate. 28. 8 Benzylurea 30. 0 3-benzyl-5,6d1methylu.racil. Ethyl 2-ethyl-3-ketooctanoatc 45. 4 Benzylthiourea. 33. 2 3-benzyl-Scthyl-G-amyl-Zthiouracil. Ethyl 2-mcthyl-3-ketohexanoate 34. 2 fi-phenethylurea. 32. 8 3-(fl-phcnethyl)smethyl-fi propyluracil. Ethyl Z-methyl-S-kctobu tyrate 28. 8 Furt'urylurea 28.0 S-furfuryl-5.6-dimethyluracil.

D0 28. 8 Tert.-amylurea 26. 0 3-tert.-amyl-5,6-dimethyluraeil. Do 28. 8 1-(hcxahydro-4,7- 39. 0 3-(3a-4-5-6'7-7a-hexahydro-4,7-methauo-5- methano-fidndauyl) indanyl)-5,6-dimcthyluracil. urea. Do 28. 8 Phcnylurca 27. 2 3-phenyl-5,6dimcthyluracil. Ethyl 2-butyl-3-ketovalcratc 39. 8 p-cliilorophenyl- 37. 2 3-(p-ch10rophcuyl)-5-butyl-6-cthyl-2-thioureciL.

t iourca. D0 34. 2 m-Tolylurea 30. 0 3-(m-tolyl)5,6-diethyluracll. Ethyl 2-methyl-3-ketooctanoate 39. 8 p-Anisylurea 33. 2 S-(p-auisyl)-5-methyl-6-amyluracll. Ethyl 2-ethyl-3-kctobutyrate 31. 4 o-Nitrophcnylthiour a 39. 4 3-(o-nitrophcnyl)-5-othyl-o-mcthyl'2-thiourac1l. Ethyl 2-mcthyl-3-ketobutyrate 28. 8 Octyn-7-ylurea 33. 6 3-(octyu-7-yl)-5,6-dimethyluracil. Ethyl 2-propyl-3-kctohcxanoate, 39. 8 Allylurea 20. 0 3-allyl-5,6dipropylu.racil. Ethyl 2-mcthyl-3-kctobutyrate. 28. 8 fl-phcnethylthiourea. 36. 0 3-(fl-phencthyl)-5.6-dimcthyl-2thiouraoil. Ethyl 2-fluoro-3-ketobutyratc 29. 4 Sec-butylurea 23. 5 3 .-butyl-5-fluoro-6-methyluracil.

D0 29. 4 2-(5-iudanyl) cthylurea 38. 0 (5-indanyl)cthyl -5-fiuoro-6-mcthyluracil. thyl 2-111ethyl-S-ketobutyrate 28.8 Cyclopeutenylurea 25.8 3-cyclopcntcnyl-5,6- imcthyluracil.

21 Example 1] .Preparation 3-cycl0hexyl-5- hydroxymethyl-6-meflzyluracil A mixture of 208 pants by weight of 3-cyclohexyl-6- methyluracil, 1400 parts by weight of water, 315 parts by weight of ethyl alcohol, 66 parts by weight of paraformaldehyde, and 20 parts by weight of barium hydroxide is heated until the components are completely dissolved. The solution is then stripped and the oil which remains is extracted with ether. This ether extract is dried with magnesium sulfate, filtered, and concentrated at reduced pressure to a slightly gummy solid. This solid is recrystallized from acetonitrile to give 3-cyclohexyl-5-hydroxymethyl-6-methyluracil, melting at 175-176 C.

The following compounds are similarly prepared by substituting equivalent amounts of the designated uracil starting reactants for 3-cyclohexyl-6-metl1y1uracil:

anol, and the solution is filtered free of the inorganic salts. Ten parts of ohloroacetic acid are added to the solution and it is charged into a bomb and heated at 125 C. for 5 hours.

filtered :hot and concentrated to an oil.

The oil is dissolved in 250 parts of methanol and chilled to about -50 C. Pure, white 3-isopropyl-5-methoxy- It is filtered off and methyl-o-methyluracil precipitates. dried. It melts at 1l6.5 C. to 11S.5 C.

Example 15.Preparation of 3-is0propyl-5 metlzyltlziometllyl-dmethy/uracil Uracil starting reactant 5-hydroxyalkyluracil products 3-is0propy1-6-methyluracil 3-cyclohexy1-6-ethyl-2-thiouraci1 3(bieyclo[2,2,2]oct5-en-2-y1)-6-methyluraci1 3benzyl-6-mcthyluraoil 3-cylcopeutenyl-6-propyluracil 3-(m-cthylbicyclo[2,2,2]oct-5-en-2-yl-methyl)-6-methyluracil 3 1 1- dhnethylpropyl) -6-ethyl-2-th iouracil 3- (p-chlorophenyl -6-butylura oil 3-allyl-6-methyluracil 3- (hexahy dro-fi-indcuylmethyl) -6-m ethyluraci 3- (7-bromo4-in denyD-fi-methyluraeil 3-(hexahydro-l-indenyl)-6-methy1uracil 3-(1 ,4, 5, 6-tetrachloro-7, 7-dimethoxy bicyclo [2, 2, 1]hept-5-en-2-yl-methyl) -6- methyluraeil.

3-(5,6,7,8,10,IO-hexachloro-l,2,3,4,4a,5,8,8a0ctahydro-1,45,8-dimethano-2- naph thyl) -6-methyluracil.

3- (5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-methanO-Z-naphthyl) -6-ethyluraeil.

3- (5,6,7,8,9,Q-hexachloro-l,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2-naphthyl) bencthyluracii.

3- (5,6 ,7 ,S-tetrachloro-decahy dr0-10, IO-dimethoxy-l ,4'5, S-dimcthano-Z- naphthyl) -6-1nethyluracil.

3-(5,6,7,8,l0,IO-hexachloro-dceahydro-1,4-5,8-dimethano-Z-naphthyl)-6- methyluracil.

3- (3 a ,4, 5,6, 7,7a-hexahydro-4, 7-mcthano-5-indanyl) -6-methy1uracil Example 12.Preparation of 3-isopr0p0pyl-5- methOxymethyl-6methyluracil To a warm solution of 21.7 parts by weight of S-ehloromethyl-3-isopropyl-6-methyluracil in 150200 parts by weight of methanol is added 5.4 parts by weight of sodium methoxide. The solution is heated to reflux for minutes. The methanol is then evaporated, and the product extracted with ether. Evaporation of the ether yields 3- isopropyl-S-rne-thoxymethyl-6-methyluracil in a crystalline state.

Example 13.-Preparati0n 0f 3-is0pr0pyl-5- methylthiomethyl-o-methyluracil A suspension of 21.7 parts by Weight of S-chloromethyl- 3-isopropyl-fi-methyluracil and 7.0 parts by weight of sodium methylmercaptide in 100 parts by weight of tetrahydrofuran is heated to reflux for 45 minutes while gaseous methyl-mercaptan is added at a slow rate. The solvent is then evaporated and the product extracted from the residue with ether. Evaporation of the ether yields the desired 3-isopropyl-5-methylthiomethyl-G-methyluracil in a crystalline state.

Example 14.Preparati0n of 3-is0pr0pyl-5- metlzoxymethyl-6-methyluracil A mixture of 168 parts of 3-isopropyl-6-methyluracil, 1400 parts of water, 375 parts of ethanol, 66 parts of pformaldehyde and parts of barium hydroxide is heated and stirred at reflux for A2 hour or until a fine solid begins to precipitate. The solution is chilled, neutralized with dilute hydrochloric acid, and concentrated to a viscous oil at reduced pressure at 50-80 C.

The oil (194 parts) is stirred with 500 parts of methshaken and heated at 125 C. for 5 hours.

and parts of methyl mercaptan.

cooled and poured into 7000 parts of ice and water.

The white solid which precipitates is filtered off and recrystallized from acetonitrile or nitromethane giving pure 3-isopropyl-S-methylthiomcthyl-6-methyluracil.

The following compounds are prepared as in Examples 12, 13, 14 and 15 by substituting equivalent amounts of the appropriate substituted uracils and equivalent amounts of appropriate alkoxides, alkylmcrcaptides or arylmercaptides for the substituted uracils and sodium methoxide or alkylmercaptide in Examples 12 and 13, or by employing the alternate routes described in Examples 14 and 15. Equivalent amounts of hydrogen sulfide can be substituted for methyl mercaptan in Example 15 to give the corre sponding 5-mercaptomethyl substituted uracil.

3 -cyclohexyl-5-methoxymethyl-6-methyluracil 3 -cyclooctyl-5-methylthiomethyl-6-ethyl-2-thiouracil 3-cyclohexyl-5-sec.-amyloxymethyl-6-chlorouracil 3 -octyl-5 -propoxymethyl-6-methy1uracil 3-pheny1-5-methoxymethyl-6-methyluracil 3- (p-chlorophenyl) -5-ethoxymethyl-6-propyluracil 3 -allyl-5-ethoxymethyl-6-ethyl-2-thiouracil 3 -benzyl-5-ethylthiomethyl-6-methyluracil 3 -cyclopentenyl-S-methylthiomethyl-6-methyluracil 3 -butyl-5-methoxymethyl- 6-ethyluracil 3-tert.-butyl-5-methoxymethyl-6-methyluracil 3 -norbornenyl-5-methoxymethyl-S-methyluracil 3 -cyclohexyl-5-mercaptomethyl-6-methyluracil 3 -cyclohexyl-5-carboxymethylthiomethy-l-6-methyluracil 3 -octyn-2-yl-5-methoxymethyl-6-methyluracil 3- (2,3 -dich1oro-2,3 ,4,5,6,7,7a-hexahydro-4,7-methanoindanyl) -S-methoxymethyl-6-methyluracil The reaction mixture is concentrated to an oil, which is taken up in 400 parts ot acetonitrile, refluxed for a short time with 5 parts of decolorizing carbon,

An autoclave is charged with 198 parts of S-hydroxymethyl-3-isopropyl-fi-methyluracil, 1500 parts of methanol The mixture is It is then 3 (3 a,4,5,6,7,7a-hexahydro-4,7-methanoS-indenyl -5- indanyl-methoxymethyl-6-methyluracil 3-decahydronaphthyl-S-methoxymethyl-6-methyluracil 3-boryl-5-methoxymethyl-6-methyluracil 3- (5,6,7,8-tetrahydronaphthl-yl -5-methoxymethyl-6- methyluracil 3-( l,Z-dimethylcyclopentyl)-5-ethoxymethyl-G-methyluracil 3 -isopropyl-5-phenylthiomethyl-6-methyluracil 3 -cyclohexyl-5 -phenyltl1iomethyl-6-methyluracil 3 5,6,7, 8,9,9-hexachloro- 1 ,2,3 ,4,4a,5 ,8,8a-octahydro-5 ,8-

methano-Z-naphthyl -5-methoxymethyl-6-methyluracil 3-(5,6,7,8,10,10-hexachloro-l ,2,3 ,4,4a,5,8,8a-octahydro- 1,4-5 ,8-dimethano-2-naphthyl) -5-methoxymethyl-6- methyluracil 3- 3 a,4,5,6,7,7a-hexahydro-4,7-methano-5-indanyl -5- methoxynrethyl-G-methyluracil 3-norbornyl-S-methylthiomethyl-6-methyluracil 3 -fenchyl-S-methoxymethyl-6-rnethyluracil 3-o-methylcyclohexyl-S-methoxymethyl-6-methyluracil Example 16.-Preparation of 3-is0pr0pyl-5-chloromethyl- 6-metlzyllzracil A mixture of 17 parts by weight of 3-isopropyl-6- methyluracil and 38 parts by weight of chloromethylmethyl ether is heated in an autoclave under endogenous pressure at 100 C. for 25 hours. The material is cooled and the excess reagent evaporated under vacuum. The product is extracted from the residue with dry dioxane. The dioxane is then evaporated to dryness, leaving essentially pure 5-chloromethyl-3-isopropyl-6-methyluracil as a residue.

Example 17.Preparatin of -chloromethyl-3-is0propyl- 6-methyluracil To 452 parts of rapidly stirred thionyl chloride, maintained below 25 C. with an ice bath, are gradually added 198 parts of 5-hydroxymethyl-3-isopropyl-6-methyluracil. Caution should be used in carrying out this reaction because of the large amounts of acidic gases produced and the vigor of the reaction.

An efficient condenser is used to retain the thionyl chloride reactant, and a scrubber is used to wash away the gases produced.

When a complete solution has been obtained, it is distilled to dryness at reduced pressure at 50 C. The solid is triturated with 200 parts of a 1:1 mixture of 1,1,2-trichloroethane and heptane, and filtered.

The solid is then recrystallized from 600 parts of the same solvent, giving pure 5-chloromethyl-3-isopropyl-6- methyluracil, M.P. 151.5 C. to 153 C.

The following S-halomethyluracils can be prepared by the method of either Example 16 or 17 by substituting an appropriate uracil for the 3-isopropyl-6-methyluracil of Example 16, or by substituting an appropriate thionyl halide and substituted uracil for the thionyl chloride and 5-hydroxyrnethyl-4-isopropyl-6-rnethyluracil of Example 17:

3 -cyclohexyl-5-chloromethyl--methyluracil 3-(p-anisyl -5-chloromethyl-6-propyl-2-thiouracil 3-propynyl-5-chloromethyl-6-ethyluracil 3-0ctyl-5-c hloromethyl-6-methyluracil 3-sec.-butyl-6-bromo5-chloromethyluracil 3- fi-phenethyl 5 -chloromethyl-6-methyl-2-thiouracil 3 -isoamyl-5-chloromethyl-6-butyluracil 3-(m-nitrophenyl)-5-chloromethyl-6-methyluracil 3-cyclohexyl-5-brornomethyl-6-methyluracil 3-cyolohexyl-5-fiuoromethyl-6-methyluracil 3 -sec.-butyl-5-fluoromethyl-G-methyluracil 3-sec.-butyl-5-bromomethyl-6-methyluracil Example 18.Preparation of 3-sec.-butyl-6-methyl-5- thiocyanatouracil A mixture of 182 parts of 3-sec.-butyl--methyluracil, 700 parts of acetic acid and 152 parts of ammonium thio- 24 cyanate is stirred at 10 C. to 15 C; as parts of bromine dissolved in parts of acetic acid are gradually added over a period of 2 to 4 hours. When the addition is complete, the reaction is stirred for a short time at 15 C. to insure completion, and then diluted with 9000 parts of ice and water.

The mixture is extracted with 4000 parts of dichloromethane. The organic layer is separated, filtered free of polymeric material, washed with sodium bicarbonate solution, dried over magnesium sulfate, filtered and concentrated to dryness at reduced pressure.

The solid residue is triturated with cyclohexane and filtered. It is recrystallized from 1,1,2-trichloroethane to give pure, white 3-sec.-butyl-6-methyl-5-thiocyanato uracil, M.P. 157 C. to 158 C.

Example 19.-Preparatian of 3-pentyl-6-methyl-5-thi0- cyanato-Z-tlziouracil A suspension of 39 parts by weight of ammonium thiocyanate in 200 parts by volume of carbon tetrachloride is treated slowly and with vigorous agitation with 17.6 parts by weight of bromine. Occasional external cooling is required to hold the temperature of the reaction mixture at 15-20 C. At the end of the addition, stirring is continued until the bromine color is discharged, after which the solution is filtered rapidly, preferably in the absence of moisture. To this solution is added 21.2 parts by weight of 3-pentyl-6-methy1-2-thiouracil, and the resulting mixture is stirred at room temperature for 5 hours. At the end of this time, the solvent is removed, leaving behind essentially pure 3 pentyl-6-methyl-5-thiocyano-2-thiouracil.

The following compounds are similarly prepared by substituting equivalent amounts of the appropriate uracil starting reactants for 3-pentyl-6-methyl-2-thiouracil:

3 cyclopentenyl-6-methyl-S-thiocyanatouracil 3 -heptyl-6-ethyl-5-thiocyanato-2-thiouracil 3 -norbornyl-6-methyl-S-thiocyanatouracil 3-(m-nitrophenyl)-6-butyl-5-thiocyanatouracil 3-benzyl-6-methyl-S-thiocyanatouracil 3- ,B-phenethyl -6-methyI-S-thiocyanatouracil 3-cyclohexyl-6-methyl-5-thiocyanatouracil 3 -cyclopentyl-G-butyl-S-thiocyanatouracil 3 -cycloheptenyl-6-ethyl-5-thiocyanato-2-thiouracil 3 -isopr-opyl-6-methyl-5-thiocyanatouracil 6-methyl-3 -phenyl-5-thio cyanatouracil Example 20.Preparati0n of 5-chlor0-6-chl0r0methyl-3- isopropyluracil A mixture of 168 parts of 3-isopropyl-G-methyluracil, 100 parts of acetic acid and 650 parts of water is vigorously stirred as 147 parts of chlorine are gradually added as a gas. The temperature is maintained at 30 C. to 35 C. with a cooling bath.

The white slurry is stirred for an additional hour and 400 parts of concentrated hydrochloric acid are then added gradually with stirring. The slurry is heated at refiux for 5 hours, chilled to about 20 C. and filtered. The filter cake is resuspended in 500 parts of cold water and refiltered.

The dry filter cake is recrystallized from acetonitrile to give S-chloro-6-chloromethyl-3-isopropyluracil, M.P. 186 C. to 188 C.

The following compounds are similarly prepared by substituting equivalent amounts of the appropriate uracil starting reactants, halogen, and halogen acid for the 3- isopropyl-G-methyluracil, chlorine and hydrochloric acid:

5 -bromo-6-bromomethyl-3 -is'opropyluracil 5-chloro-6-chloromethyl-3-cyclohexyluracil 5-chloro-6-chloromethyl-3-pheny1uracil 5-bromo-6-bromomethyl-3-('3-chlorophenyl)uracil 3 -sec.-butyl-5-chloro-6chloromethyluracil 3-sec.-butyl-5-chloro-6-(a-chlorobutyDuracfl 3 cyclopentyl-5 chloro-6-( a-chloroethyDuracil 3 -cycloheptyl-5-chloro-6-chloromethyluracil Example 21.Preparati/t of 3-plzenyl-5-meth0xy-6- methyl-Z-zhiouracil A mixture of 34 parts of bromine and 200 parts of glacial acetic acid is added gradually at 20 C. to a stirred mixture of 21.8 parts of 3-phenyl-6-rnethyl-Z-thiouracil, 250 parts of glacial acetic acid and 200 parts of anhydrous sodium acetate. Stirring is continued until the bromine absorption is complete.

At this point, the mixture is distilled under reduced pressure to remove the acetic acid. The residue is combined with 350 parts of methanol and 130 parts of sodium methoxide and heated at reflux under anhydrous conditions for hours. Methanol is removed from the reaction by distillation and the remaining solid is added to 250 parts of glacial acetic acid.

The latter mixture is stirred while 13.0 parts of zinc dust are added over a /2 hour period. Stirring is continued for an additional half hour, then the reaction is diluted with 4 volumes of water and the solid filtered.

The solid is extracted with 200 parts of 1 Normal sodium hydroxide solution and acidification of the basic filtrate gives essentially pure 3-phenyl-5-methoxy-6- methyl-2-thiouracil.

The following compounds can be prepared in a similar fashion by substituting equivalent amounts of the appropriate thiouracil starting reactant and sodium alkoxide or sodium mercaptide for the 3-phenyl-6-methy1-2-thiouracil and sodium methoxide:

3-isopropyl-S-methoxy-6-methyl-2-thiouracil 3-sec.-butyl-5-metl1oxy-6-methy1-2-thiouracil 3 -cyclohexyl-S-rnethoxy-6-methyl-2-thiouracil 3-decahydronaphth-1-yl-5-methoxy-6-methyl-2-thiouracil 3-(3a,4,5,6,7,7a-hexahydro-4,7-methano-5-idenyl)-5-methoxy-6-methyl-2-thiouracil 3-tert.-butyl-5-butoxy-G-methyl-Z-thiouracil 3 -isopropyl-5-isopropoxy-6-methyl-2-thiouracil 3-norbornyl-S-rnethoxy-6-rnethyl-2-thiouracil 3-isopropyl-5-methylthio-6-methyl-2-thiouracil 3-sec.-butyl-5-butylthio-6-methyl-2-thiouracil 3 -cyclohexyl-S-isopropylthio-6-methyl-2-thiouracil Example 22.Preparation 0f 3-cyclolzexyl-5-meth0xy- 6-methyluracil A total of 25.4 parts or 3-cyclohexyl-5-methoxy-6- methyl-Z-thiouracil and 250 parts of 2 Normal sodium hydroxide is stirred rapidly as 14.0 parts of dimethylsulfate are added gradually over a period of /2 hour. A product forms which is collected and added to 200 parts of a 10% solution of chloroacetic acid.

The resulting mixture is heated With rapid stirring at reflux temperature for a 2 hour period. The entire reaction is then cooled and filtered, yielding essentially pure 3-cyclohexyl-S-methOXy-Gmethyluracil.

The following compounds can be prepared in a like fashion by substituting equivalent amounts of the appropriate thiouracil starting reactant for 3-cyclohexyl-5-methoxy-6 -methyla2-thiouracil:

3-norbornyl-5-methoxy-6-methyluracil 3-tert.-butyl-5-butoxy-6-methyluracil 3-decahydronaphth-1-yl-5-methoxy-6-methyluracil 3-isopropyl-5-methoxy-6-methyluracil 3 -isopropyl-5-isopropoxy6-methyluracil 3 3a,4,5 ,6,7,7a-hexahydro-4,7-methano-5-indenyl) -5-methoxy-6-methyluracil 3-isopropyl-S-ethylthio--methyluracil 3 -cyclohexyl-5-methylthio-6-methyluracil 3-tert.-butyl-5-propylthio-6-methyluracil Example 23.Preparati0n of 5-cyaIz0-3-cycl0hexyl- 6-melhyluracil A mixture of 142 parts of cyclohexylurea, 178 parts of triethyl orthoacetate and 72 parts of malononitrile is 26 stir-red at reflux for two hours, The volatile substances are distilled oil at reduced pressure giving a solid residue of [1-(3-cyclohexylureido)ethylidene]malononitrile, which is recrystallized from aqueous ethanol.

A mixture of 218 parts of thio[l-(3-cyclohexylureido) ethylidene1malononitrile, 700 parts of methanol and 54 parts of sodium methoxide is protected from atmospheric moisture and allowed to stand at room temperature for five days. The alcohol is removed by distillation at reduced pressure at room temperature, and the resulting solid is dissolved in 2000 parts of cold water. Acetic acid is gradually added until the mixture is slightly acidic.

The 3-cyclohexyl-6-methyl-5-cyanocytosine which precipitates is filtered off, Washed with water, dried, and recrystallized from ethanol.

Two hundred and thirty-two parts of this 3-cyclohexyl- -methyl-S-cyanocytosine are dissolved in 1430 parts of 3 Normal hydrochloric acid, and the solution is refluxed for 3 hours. After cooling, the resulting white solid 5-cyano-3-cyclohexyl-6-methyluracil is filtered ofl? and recrystallized from ethanol.

The following 3,6-disubstituted-S-cyanouracils can be prepared in the same fashion by substituting an appropriate urea for cyclohexyl urea and an appropriate triethyl o-rthoester for the triethyl orthoacetate:

5-cyano-3-isopropyl-6-methyluraci1 3-sec.-butyl-5-cyano-6-methyluracil 5-cyano-6-methyl-3-norbornyluracil 5 cyano-6-methyl-3-phenyluracil 5-cyano-6-methyl-3 -phenyluracil 3 -cyclohexyl-S-cyano-6-methyluracil Example 24.-Preparation of 3-cycl0hexyl-5-(Z-hydroxyethyl )-6-methyluracil A mixture of 426 parts by weight of cyclohexylurea, 423 parts by weight of Z-acetylbutyrolactone, 879 parts by weight of benzene, 1030 parts by weight of dioxane, and 40 parts by weight of phosphoric acid is stirred at reflux temperature.

The water given off is removed by azeotropic distillation. When no more water is given off, the solution is cooled, decanted, and concentrated to dryness under reduced pressure. Three recrystallizations of the resulting solid from acetonitrile give 2-(2-hydroxyethyl)-3-cyclohexylureido)crotonic acid, -lactone.

A mixture of 302 parts by weight of the 2-(2-hydroxyethyl)-3-(3-cyclohexylureido)crotonic acid, 'y-lactone, 1580 parts by weight of absolute ethanol, and 130 parts by weight of sodium methoxide is refluxed for 15 minutes. It is then concentrated to dryness at reduced pressure, and the residue is dissolved in 1500 parts by weight of water.

This solution is cooled, acidified with hydrochloric acid to pH 5, and the resulting white precipitate, 3-cyclohexyl- 5-(2-.ydroxyethyl)-6-methyluracil, is filtered oif, dried, and recrystallized from a mixture of ethanol and water.

The following uracils are similarly prepared by replacing the cyclohexylurea with equivalent amounts of appropriate ureas and by replacing 2-acetylbutyrolactone, where indicated, with equivalent amounts of the corresponding homologues:

5- (Z-hydroxyethyl)-3-isopropyl-6-methyluracil 5- 2-hydroxyethyl -6-methyl-3-phenyluracil 5- Z-hydroxypropyl -6-methyl-3 -norbornyluracil 3-sec.-butyl-5-(2-hydroxyhexyl)-6-methyluracil Example 25.Preparati0n 0f 3-butyl-5-chl0r0-6- methyluracil, sodium salt A solution of 4 parts of sodium hydroxide in parts of water is treated with 21.7 parts of 3-butyl-5-chloro-6- methyluracil. Stirring and Warming is employed to eflect solution. The water is removed from the solution under reduced pressure, leaving 3-butyl-5-chloro-6-methyluracil, sodium salt, as a white solid.

The metal salts of the compounds prepared according to the foregoing examples can be prepared as in Example 25 by substituting equivalent amounts of other substituted uracils and other metallic hydroxides for the 3-butyl-5- chloro-6-methyluracil and sodium hydroxide. The following list contains examples of salts prepared in this fashion:

3-scc.-butyl-5-chloro-6-methyluracil, sodium salt 3-butyl-5-bromo-6-methyluracil, potassium salt 3-hexyl-5-chloro-6-ethyluracil, 1/2 calcium salt 3-phenyl-5-chloro-6-methyluracil, sodium salt 3- (m-fluorophenyl) -5-bromo-6-methyluracil, 1/2 magnesium salt 3-(p-cumyl)-5-chloro-6propyluracil, potassium salt S-(fl-phenethyl)-5-bromo-6-butyluracil, 1/ 2 calcium salt 3-allyl-S-chloro-6-methyl-2-thiouracil, strontium salt 3-isoamyl-5-bromo-6-methyluracil, potassium salt 3 (3a,4,5,6,7,7a hexahydro-4,7-methano-5-indanyl)-5- bromo-6-methyluracil, sodium salt 3-(p-chlorophenyl)-5-nitro-6-propyluracil, l/ 2 barium salt 3-al]yl-5-bromo-6-methyluracil, lithium salt 3-isopropyl-5-bromo-6-methyluracil, sodium salt 3-isopropyl-5,6-dimethyl-2-thiouracil, sodium salt 3-propynyl-5-methyl-6-butyluracil, potassium salt 3-benzyl-5,6-dimethyluracil, iron salt 3-sec.-butyl-5-chloro-6-methyluracil, 1/2 calcium salt 3-sec.-butyl-5-bromo-6-methyluracil, sodium salt 3-phenyl-5,G-dimethyluracil, sodium salt 3-(p-anisyl)-5-methyl-6-amyluracil, sodium salt 3-allyl-5,6-dipropyluracil, l/ 2 magnesium salt 3-sec.-butyl-5-nitro-6-methyluracil, sodium salt 3-benzyl-5-methoxy-6-propyl-2-thiouracil, l/2 barium salt 3-phenyl-5-methoxy-6-methyluracil, sodium salt 3-butyl-6-methyl-5-thiocyanouracil, manganous salt 3-phenyl-6-butyl-S-thiocyanouracil, 1/2 calcium salt 3-phenyl-5-bromo-6-methyluracil, sodium salt 3-sec.-butyl-5-bromo-6-methyluracil, potassium salt 3 (1,1 dimethylbutyl)-5-chloro-6-methyluracil, sodium salt 3-phenyl-5-bromo-6-methyluracil, potassium salt 3-phenyl-5-bromo-6-methyluracil, lithium salt 3-norbornyl-5-bromo-6-methyluracil, potassium salt 3 norbornenyl-5-hydroxymethyl-6-methyluracil, 1/2 calcium salt 3-cyclopentenyl-5,6-dimethyluracil, 1/2 calcium salt 3-cyclopropylmethyl-5-bromo-6-methyluracil, sodium salt 3-cyclohexyl-5-methoxy-6-methyluracil, sodium salt 3-isopropyl-5-nitro-6-methyluracil, sodium salt 3-(m-tolyl)-5-bromo-6-methyluracil, sodium salt 3-(m-chlorophenyl)-5-chloro-6-methyluracil, sodium salt 3-cyclohexyl-5-bromo-6-methyluracil, sodium salt 3-cyclohexyl-5-chloro-6-methyluracil, sodium salt 3-cyclopentenyl-5-chloro-6-isobutyluracil, 1/ 2 calcium salt 3-cyclohexyl-5-fluoro-6-methyluracil, potassium salt 3-cyclohexyl-6-methyl-5-nitrouracil, sodium salt 3 cyclopentenyl-5-methylthiomethyl-6-methyluracil, lithium salt 3-cyclohexyl-6-methyl-5-thiocyanouracil, sodium salt 3-tert.-butyl-5-chloro-6-methyluracil, sodium salt 3 (l-ethyl propyl)-5-bromo-6-methyluracil, potassium salt 3-tert.-butyl-S-chloro-6-methyluracil, sodium salt 3-allyl-5-allyl-6-propyluracil, sodium salt Example 26.Preparation of 1 :1 complex of 5-brom0-3- isoprpyl-6-methy[uracil and pentachlorophenol A mixture of 247 parts of -bromo-3-isopropyl-6-methyluracil, 266 parts of pentachlorophenol and 1250 parts of cyclohexane is stirred at reflux as 50 parts of nitromethane are gradually added. The physical appearance of the solid changes rapidly. When no further change is noticed, the mixture is chilled and the solid product is filtered off and recrystallized from nitromethane. The complex melts at 142-143 C.

The following complexes can be prepared in a similar fashion by substituting equivalent amounts of the proper phenol and uracil for the 5-brom0-3-isopropyl-6-methyluracil and pentachlorophenol:

1:1 complex pentachlorophenol and 5-bromo-3-sec.-butyl- 6-methyluracil 1:1 complex pentachlorophenol and 5-bromo-3-tert.-butyl- 6-methyluracil 1:1 complex pentachlorophenol and 5-bromo-3-(2-methylbutyl)-6-methyluracil 1:1 complex m-methylphenol and 5-bromo-3-sec.-butyl- 6-methyluracil 1:1 complex p-nitrophenol and 5-bromo-3-sec.-butyl-6- methyluracil 1:1 complex phenol and 3-isopropyl-5-nitro-6-methyluracil 1:1 complex p-methoxyphenol and 5-bromo-3-sec.-butyl- 6-methyluracil Example 27.Preparati0n of 2:] complex of 5-bromo-3- isopropyl-6-methyluracil and phenol A dry mixture of 247 parts of 5-bromo-3-isopropyl-6- methyluracil and 47 parts of phenol is gradually heated until a clear melt is formed. This is stirred for a short time to insure complex formation, and then cooled. The resulting solid cake, M.P. l40.5l42 C., is sufficiently pure for incorporation into herbicidal formulations.

The following complexes can be formed by substituting molecularly equivalent quantities of the appropriate phenols for phenol, and the appropriate uracils for S-bromo- 3-isopropyl-6-methyluracil:

Example 28.Preparation of 2:] complex of 5-bromo-3- isopropyl-6-melhyluracil and phenol A mixture of 247 parts of 5-bromo-3-isopropyl-6-methyluracil, 1200 parts of cyclohexane and 47 parts of phenol is refluxed with stirring for from 5 to 30 minutes. This slurry is filtered while hot, and the solid filter cake is recrystallized from 300 parts of nitromethane. The pure 2:1 solid complex thus formed is filtered oil, and dried at room temperature in air.

Example 29.Preparation of the ethanolamine addition compound of 5-brom0-3-isopropyl-6-methyluracil A solution is prepared by mixing together 247 parts of 5-bromo-3-isopropyl-6-methyluracil, 392 parts of acetonitrile and 61 parts of ethanolamine. The solvent is distilled oil at reduced pressure and the oil which remains gradually solidifies. The molar addition compound is recrystallized from nitromethane; it melts at -83" C.

Example 30.Preparation of the octylamine addition compound of 5 -bromo-3-isopropyl-d-methylaracil A mixture containing one part of octylamine and one part of S-bromo-3-isopropyl-6-methyluracil is stirred and maintained at about 40 C. with gentle heating until the ingredients are in complete solution. The solution is cooled and the hard granular crystals which form are filtered off and washed three times with small portions of cold benzene. The resulting molar addition compound melts at 74-78 C.

Example 31.Preparali0n of the ethylenediamine addition compound of 5 -bl'omo-3-isopropyl-6-melhyluracil Two hundred and forty-seven parts of 5-bromo-3-isopropyl-G-rnethyluracil are dissolved in 300 parts of acetonitrile at ambient temperature. Sixty parts of ethylenediamine are added and the mixture is stirred vigorously. The solid white addition compound which gradually precipitates is filtered off and dried at room temperature under reduced pressure. The addition compound melts at 102-l06 C. It can be further purified by recrystallization from acetonitrile if desired.

The following addition compounds are prepared according to any of the procedures of Examples 29, 30 and 31 by substituting molar equivalents of a properly substituted uracil'and an apppropriate amine for -bromo-3- isopropyl 6 methyluracil, ethanolamine, octylamine or ethylenediamine:

5 -bromo-3 -sec.-outyl-6-methyluracil ethanolamine addition compound 3 -sec.-butyl-S-chloro-6-methyluracil ethanolarnine addition compound 5-bromo-3-sec.-butyl-6-methyluracil ethylenediamine addition compound S-bromo-3-sec.-butyl-G-rnethyluracil dodecylamine addition compound 5-bromo-3-sec.-butyl-6-methyluracil-cocoadiamine addition compound 5 -bromo-3 -isopropyl-6-methyluracil dodecylamine addition compound 5-chloro-3-isopropyl-drnethyluracil-ethanolamine addition compound 5-bromo-3-tert.-butyl-6-methyluracil-ethanolamine addition compound S-bromo-3-tert.-butyl-6-methyluracil-dodecylamine addition compound 5,6-dimethyl-3-isopropyluracil ethanolamine addition compound 5,6-dimethyl-3-isopropyluracil-dodecylamine addition compound 5-bromo-6-rneth yl-3-phenyluracil ethylenediamine addition compound 5-bromo-6-methyl-3-phenyluracil dodecylamine addition compound 5-chloro-6-1iethy1-3 -phenyluracil ethanolamine addition compound 3-isopropybfi-methyl-5-nitrouracil ethanolamine addition compound 5-bromo-6-methyl-3 -sec.pentyluracil ethanolamine addition compound 5 -bromo-3 3-chlorophenyl -6-rnethyluracil piperidine addition compound 5-bromo-6-methyl-3-norbornyluracil:piperidine addition compound 3-isopropyl-6-methyl-5-nitrouracil ammonia addition compound 3 -isopropyl-6-methyl '5-nitrouracil methylamine addition compound 5-brorno-6-ethyl-3-isopropyluracil ethanolamine addition compound Example 32.-Preparati0n of the tetmbuty[ammonium salt 0 5,6-dimetlzyl-S-isopropyluracil A total of 182 parts of 5,6-dirnethyl-3-isopropyluracil is gradually added, with stirring, to 1000 parts of a one molar solution of tetrabutylammonium hydroxide in methanol. When solution is complete, the solvent is distilled off at reduced pressure. The While solid tetrabutylammonium salt of 5,6-dimethyl-3-isopropyluracil which remains is sufliciently pure for incorporation into herbicidal formulations.

The following tertaalkylarmnoniuin salts can be similarly prepared by substituting molar equivalent amounts of a properly substituted uracil and an appropriate quaternary ammonium hydroxide for 5,6-dimethyl-3-isopropyluracil and tetrabutylamrnonium hydroxide:

Tetramethylarnmoniurn salt of 3-tert.-butyl-5-chloro-6- methyluracil Tetramethylammonium salt of 3-sec.-butyl5-chloro-6- methyluracil Tetramethylammonium salt of 3-sec.-butyl-5,S-dimethyluracil Tetramethylammonium salt of 5-bromo-3-sec.-butyl-6- methyluracil Tetramethylammonium salt of 5-bromo-3'(2-rnethylpropyl)-6-methyluracil Tetrabutylammonium salt of 3-isopropyl-6-methyl-5- nitrouracil Tetrabutylamrnonium salt of 3-sec.-butyl-6-methyl-5- nitrouracil Tetrabutylammonium salt of 5-bromo-6-methyl-3- phenyluracil Tetrabutylammonium salt of 5-chloro-6-methyl-3- phenyluracil Tetrabutylammonium salt of 5,6-dimethyl-3-phenyluracil Tetrabutylammonium salt of 5-bromo-3-(3-chlorophenyl -6-methyluracil Tetrabutylammonium salt of 5-bromo-6rnethy1-3- norbornyluracil Trimethyldodecylammonium salt of 5-chloro-3cyclohexyl-6-methyluracil 1,1'-ethylene-2,2'-dipyridinium salt of -di-(5-bromo3- isopropyl-6-methyluracil) Trimethyldodecylammonium salt of 5bromo-3-isopropyl- 6-methyluracil FORMULATIONS LIQUID COMPOSITIONS AQUEOUS SOLUTIONS Example 33 Percent 3-cyclopentyl-5-chloro-6-methyluracil, Na salt 20 Sodium lauryl sulfate 2 Water 78 The solution is prepared by dissolving the two soluble salts in the Water, with agitation. This solution is suitable for quick dilution to desired spray levels.

Other soluble salts suitable for preparation of water concentrates are 3-sec.-butyl-5-bromo-6-methyluracil, sodium salt 3-isopropyl-5-methoxy-6-propyluracil, tetrabutylammonium salt 3-isopropyl-5-bromo-6-methyluracil, sodium salt 3-isopropyl-5-bromo-6-rnethyluracil, trimethyldodecylammonium salt This aqueous solution is used for post-emergence Weed control. A concentration of 1.0 pound of active ingredient per acre in 30 gallons of water gives excellent control of crabgrass, pigweed, velvetweed, and floWer-of-an-hour.

At concentrations of 10 to 20 pounds per acre in 80 gallons of Water, this composition gives excellent control of a Wide variety of annual and broadleaf Weeds growin g in railroad yards on railroad ballast.

Example 34 Percent 5-bromo-3-isopropyl-6-rnethyluracil 50 Ethanolamine 50 The components are mixed together at room temperature until a clear solution is formed. This solution is infinitely extendable with Water and can be diluted to any concentration.

Ten pounds of this formulation are mixed with 60 galions of Water in a spray tank. Ten pounds of trimethylnonyl ether of polyethylene glycol, are added. Only slight agitation is required for complete mixing.

Sixty gallons of this solution are applied to an acre of roadside. Excellent initial kill of foliage and residual weed control is obtained. Such species as wild oats, cheatgrass, crabgrass, foxtails, ryegrass, volunteer small grain and Wild mustard are controlled.

31 The following uracils can be substituted, in equivalent amounts, for -bromo-3-isopropyl-6-methyluracil, with excellent results:

3-scc.-butyl 5-bromo-6-methyluracil 3-tert.-butyl-5-bromo-6-methyluracil 3-cyclohexyl-5,6-dimethyluracil AQUEOUS SUSIENSIONS AND DISIERSIONS Example 35 Percent 3-cyclohexyl-5,6-dimethyluracil 28.0 Sodium lignin sulfonate 15.0 Hydrated attapulgite 2.0 Disodiurn phosphate 0.8 Sodium pentachlorophenate 0.5

Water 53.7

The above ingredients are mixed and pebble-milled or sand-milled until the average particle size of the active material is substantially less than 5 microns. The resulting stable thixotropic suspension does not cake and can be readily diluted with water to form a dilute, very slow settling suspension which requires no agitation during application.

This aqueous suspension, applied as a directed spray at 1 to 3 pounds of active ingredient per acre in 30 gallons of water, gives good pie-emergence control of barnyard grass, mustard species, and jungle rice in sugarcane.

Example 36 Percent 3-isopropyl-5,6-dimethyluracil 30.00 Sodium lignin sulfonate 15.00 Hydrated attapulgite 1.75 Anhydrous disodium phosphate 0.80 Sodium pentachlorophenate 0.50

Water 51.95

The above components are mixed together and pebblemilled or sand-milled until substantially all the active material is below 5 microns in particle size. The resulant stable aqueous suspension can be readily diluted with water to give a highly dispersd, very slowly settling composition which can be sprayed from equipment having no means for agitating the suspension.

This composition is applied at 20 pounds of active ingredient per acre in 100 gallons of water for control of annual and perennial broadleaf and grass weeds growing along pipeline rights-of-Way. Excellent control of broomsedge, crabgrass, nutsedge, Johnson grass, pigweed, goldenrod, and evening primrose is obtained.

Example 37 A water suspension is prepared by grinding the following ingredients with water in a ball or roller mill until the solids are finely dispersed in the water and the average particle size is less than 5 microns.

Percent 3-(3a,4,5,6,7,7a-hexahydro 4,7 methano-5-indenyl)- 5-hydroxymetl1yl-6-methyluracil 25 Hydrated attapulgite 2 Lignin sulfonic acids, sodium salt 5 Water 68 Example 38 A water suspension is prepared by grinding the following ingredients with water in a ball or roller mill:

Percent 3-isopropyl-5-bromo-6-methyluracil 25 Hydrated attapulgite 2 Lignin sulfonic acid, sodium salt 5 Water 68 Grinding is continued until substantially all the particles in the suspension have been reduced to diameters of less than 5 microns.

Example 39 The water suspensions of Examples 37 and 38 are useful for the control of seedling brush and annual weeds growing along fence rows. Application concentrations of 10 to 20 pounds of active ingredient per acre in 120 gallons of water give control of oak and willow seedlings, crabgrass, and chickweed.

Example 40 Percent 3-cyclohexyl-5-bromo-6-methyluracil 15.0 3-(p-chlorophenyl)-1,1-dimethylurea 15.0 Modified polyacrylic acid, Na salt 0.4 Low viscosity polyvinyl alcohol 1.0

Water 68.6

This composition is wet-milled until the particles are substantially all below 10 microns in size.

The formulation is applied in 40 gallons of water at the rate of 2 pounds (active) per acre as a directed postemergence spray for the control of young seedling annual grasses and broadleaf weeds growing in asparagus. Excellent control of crabgrass, pigweed, chickweed, bachelors button, and seedling Johnson grass is obtained.

Example 41 Percent 3-cyclohexyl-5-chloro-6-methyluracil 15 2-chloro-4,6-bis(ethylamino)-s-triazine 15 Sodium lignin sulfonate 10 Wyoming bentonite 2 Water 58 This composition is wet-milled until the particles are substantially all below 10 microns in size, to give a stable dispersion concentrate.

This formulation is useful for the control of annual and perennial boadleaf and grass weeds growing in firebreaks. An application of 20 pounds (active) per acre in gallons of water gives excellent control of pigweed, seedling bindweed, buckhorn plantain, asters, crabgrass, bromegrass, and Johnson grass.

Example 42 Percent 3-cyclohexyl-5-bromo-6-methyluracil 13.00 Pentachlorophenol 16.00 Sodium lignin sulfonate 15.00 Hydrated attapulgite 1.75 Water 54.25

These components are wet-milled until the particles are substantially all below 10 microns in size, to give a stable dispersion.

The composition is useful for the control of existing vegetation. It gives extended residual control of weeds. An application of 22 pounds (active) per acre in 100 gallons of water gives rapid initial kill of daisy, goldenrod, bouncing Bet, ragweed, brornegrasses, and annual ryegrass, with control for an extended period.

AQUEOUS CONCENTRATES Example 43 Percent 3-cyclohexyl-5,6-dimethyluracil, sodium salt 25 Sodium lauryl sulfate 1 Water 74 33 formulations, at 20 pounds of active ingredient per acre, are also useful for general control of annual and perennal weeds on industrial sites and railroad ballast.

Example 44 Percent 2-tert.-butyl-5-chloro-6-butyluracil, potassium salt 25 Sodium lauryl sulfate l Water 74 The concentrate is prepared'as a homogeneous solution by agitating the solid components in the water. It can then be readily diluted to use levels with water.

This formulation is used at 1 to 2 pounds of active ingredients per acre in 30 gallons of water for the postemergence control of annual weeds in sugar cane. A disults.

Sixty pounds of this formulation are mixed with 80 gallons of Lion Herbicidal Oil N0. 6 and applied at the rate of 15 pounds of active ingredient per acre to a weed infestation of annual and perennial broadleaves and grasses growing along a railroad right-of-way. Excellent initial contact kill of weeds, followed by good residual weed control, is obtained. Such Weed species as pigweed, ragweed, Johnson grass, broomsedge, foxtail, crabgrass, dock and wild carrot are controlled.

bromo 3 tert. butyl 6 methyluracil, 5 bromo- 3-phenyl-6-methyluracil and the 1:1 addition compound of 5-bromo-3-sec.-butyl-6-n1ethyluracil with dodecylamine can be formulated in a similar fashion, with excellent herbicidal results.

Example 46 Percent 3-sec.-butyl-5-bro1no-6-methyluracil 40 Soya lecithin 3 Substantially aliphatic, low viscosity mineral oil, e.g.,

kerosene or diesel oil 57 The oil suspension is prepared by pregrinding the active material and mixing it with the other components With agitation, or by blending all the components together, then pebble-milling or sand-milling them to reduce the particle size of the active component. The product is suitable for dilution with weed oils to form an oil spray.

This formulation is diluted with 80 gallons of an herbicidal oil such as Lion Herbicidal Oil No. 6 and applied at 12 pounds of active ingredients per acre for general over-all weed control along cyclone fences and railroad ballast.

Good control is obtained for several months. Quack grass, cheat, Witch grass, buttonweed, and Jimson weed are controlled.

Example 47 Percent 3-cyclohexyl-5-bromo-6rnethyluracil 25 Blend of polyalcohol carboxylic esters and oil-soluble petroleum sulfonates 6 Diesel oil 69 These components are mixed together and milled in a roller mill, pebble mill, or sand mill until the particles of the active component are substantially all below microns in size. The resulting suspension can be emulsified in water or diluted further with weed oils for spray application.

This formulation is diluted with 80 gallons of Lion Herbicidal Oil No. 6 and applied at 10 to 20 pounds of 34 active ingredient per acre for the control of weeds such as morning glory, chickweed, pigweed, lambs-quarter, yarrow, ragweed, wild carrot, quack grass, witchgrass,

crabgrass, and oak and maple seedlings growing along railroad rights-of-way. Excellent control is obtained.

Example 48 Percent 3-isopropyl-5 bromo-S-methyluracil 20.0 Alkyl aryl polyether alcohol 2.5 Oil soluble petroleum sulfonate 2.5 Methyl isobutyl ketone 75.0

The emulsifiable oil is prepared by mixing the above components until a homogeneous solution results. It can then be emulsified in water for application.

This emulsifiable oil is useful for weed control on railroadrights-of-way, in railroad yards, and on sidings. When this composition is diluted with 100 gallons of water per acre and sprayed from a railroad spray car at 10 pounds or" active ingredient per acre, mixed vegetation such as quack grass, cra-bgrass, Bermuda grass, bromegrass, ragweed, cockleburr, lambs-quarters, and pigweed is controlled for an extended period' Example 49 An oil suspension is prepared by grinding the following ingredients together in a ball or roller mill until the solids are finely dispersed in the oil and the average particle size is less than 5 microns.

Percent 3-benzyl-5-chloro-6-methyluracil 25 Soya lecithin 5 Aliphatic hydrocarbon oil 70 This oil suspension is applied in 50 gallons of water, at a concentration of 16-20 pounds of active ingredient per acre, as an over-all spray on a stand of established nutsedge grass.

tainedr A check of the tubers shows severe injury.

Example 50 An oil suspension is prepared by grinding the following ingredients together in a ball or roller mill until the solids are finely dispersed in the oil and the average particle size of the active ingredient is less than 5 microns.

Percent 3-(p-cumyl)-5-chloro-6-methyluracil 25 Diesel oil 67 Polyoxyethylene sorbitan ester of mixed rosin and fatty acids 8 V This oil suspension is diluted with water to form a water emulsionand is applied at a concentration of 2 pounds ofactive ingredient per acre as a directed spray to grasses growing in sugar cane. This treatment gives excellent control of mixed annular graseses and broadleaves.

Example 51 Percent 3- (p-tolyl -5-bromo-6-methyl-2-thiouracil 15 Diesel oil Polyoxyethylene sorbitan esters of mixed rosin and fatty acids 5 The oil suspension compositions of Examples 49, 50,

Excellent control of the nutsedge is ob- This oil suspension is diluted withand 51, when applied to a drainage ditch infested with mixed annual and perennial broadleaf and grass weeds at 25 pounds of active ingredient per acre in 150 gallons of water, give excellent control of vegetation. The ditch remains bare for an extended period.

These oil compositions are also useful for weed control in railroad yards and cattle yards. When diluted with 160 gallons of water per acre and sprayed from a railroad spray car at about 25 pounds of active ingredient per acre, weeds such as quack grass, crabgrass, Johnson grass, Bermuda grass, nutsedge, brome grass, ragweed, cocklebur, lambs-quarter, and mares-tail are controlled for an extended period.

Example 53 Composition I: Percent 3-sec.-butyl-5-bromo-6-rnethyluracil 25 3,4-dichlorophenyl-1,1,3-trimethylurea 25 Ethylenediamine dodecyl benzene sulfonate 2 Synthetic fine silica 48 These ingredients are blended and micropulverized.

Composition II: Percent Diesel oil 97 Mixed polyoxyethylated sonbitan tall oil ester and oil-soluble petroleum sulfonates 3 Just before use, Composition I is mixed with Composition II to form an emulsifiable dispersion containing 30% insoluble solids.

This oil dispersion controls weeds along railroad rightsof-way. An application of 12 pounds (active) in 80 to 120 gallons of water gives rapid initial kill of existing vegetation such as quack grass, goldenrod, orchard grass, bluegrass, evening primrose, and yarrow. Extended weed control is obtained with this application.

Example 54 Percent 3 isopropyl-5-bromo-6-methyluracil 25 Z-methoxy-4,6-bis'(isopro pyl-amino) -s-tniazine 50 Polyoxyethylated tert.-octyl phenol 3 Calcined montmorillonite clay 22 These components are blended and micropulverized.

The formulation is outstanding for the control of hard-to-kill perennial grasses. A spray rate of 20 pounds (active) in 80 gallons of Lion Herbicidal Oil No. 6 gives excellent control of panic grass, broomsedge, Johnson grass, and vasey grass growing along oil pipeline rightsof-way.

Example 55 Percent 3-isopropyl-5-chloro-6rrnethyluracil 40 2,4,S-trichlorophenoxyacetic acid propylene glycol butyl ether ester 10 Mixed polyoxyethylated sorbitan monooleate and ethylenediamine dodecyl benzene sul-fonate 5 Synthetic fine silica 45 These ingredients are blended, micropulverized, and reblended.

This oil dispersible powder is used to maintain weedfree areas around electric power poles by dispersing it in Lion Herbicidal Oil No. 6 and spraying it. A tweed infestation of blackberry, honeysuckle,golder 1rod, speedwell, poison ivy, pokeweed, corn cockle, crabgrass and panic grass is controlled by use of pounds (active) per acre of this fonrnulation in 80 gallons of oil.

Example 56 Percent 3-isopropyl-5-bromo-6-methyluracil 25 3 isopropyl-l-trichloromethylthio-5 bromo-6-methyluracil 50 Mixed petroleum sulfonates and polyoxyethylene tall oil esters 5 Attapulgite clay 17 Synthetic fine silica 3 These ingredients are blended and micropulverized to give an oil-dispersible powder.

This composition is extended with 100 gallons of diesel oil and sprayed at the rate of 16 pounds of active ingredient per acre. It gives excellent control of horsetail, broomsedge, Johnson grass, and quack grass along guard rails and along railroad rights-ofaway.

TANK MIXES Example 57 Ten pounds of 3-sec.-butyl-S-bromo-(Smethyluracil as an Wettable powder and 2 pounds in 4,6-dinitroorthosecondary butylphenol in 4 gallons of oil are blended as a tank mix and applied at 12 pounds of active herbicide per acre in 100 gallons of water to weeds growing along fence rows. Quick kill of annual and perennial broadleaf and grass Weeds is obtained, with excellent residual weed control.

Example 58 Twelve pounds of an 80% water-dispersible powder formulation of 3-isopropyl-5-bromo-6-methyluracil and 24 pounds of 2,2-dichloropropionic acid, sodium salt are dispersed and mixed in gallons of water.

This composition is good for the control of perennial grasses and broadleaf weeds on railroad rights-of-way.

An application of 100 gallons of this formulation per acre give good control of Johnson grass, Bermuda grass, nutsedge, crabgrass, plantain, ragweed, and beggar-tick.

Example 59 Nineteen pounds of an 80% water-dispersible powder formulation of 3-isopropyl-5-bromo-6-methyluracil or 3- sec.-butyl-5-bromo-6-methyluracil and 25 pounds of 2,2- dichlor-opropionic acid, sodium salt (85%) are dispersed and mixed in 50 to 100 gallons of water. This composition, sprayed on one .acre, gives good control of both annual and perennial grasses and broadleaf weeds growing along railroad rights-ofway and around loading dock installations.

Such difficult-to-kill weeds as crabgrass, Bermuda grass, Johnson grass, Vasey grass, nutsedge, dock, ragweed, lambs-quarters, pigweed', goatweed, carpetweed, beggartick, Spanish needle, nightshade, black medic, knotweed, plantain, spotted sponge and velvetleaf are controlled by this application.

Example 60 Ten pounds of 3-isopropyl-5-chloro-G-methyluracil as an 80% wettalble powder and 35 pounds of ammonium sul-farnate are blended as a tank mix.

An application of 45 pounds per acre (active) in 100 gallons of water controls annual and perennial broadleaf andgrass weeds growing around oil tanks and along roadsides, giving rapid contact action and extended residual weed control. Such Weeds as crabgrass, broomsedge, cocklebur, flower-of-an-hour, and oak, maple, and sweet gum seedlings are controlled by this treatment.

SOLID COMPOSITIONS DUSTS Example 6] Percent 5-bromo-6-methyl-3-(3,4-xylyl)uracil 90.0 Alkyl naphthalene sulfonate, Na salt 2.0 Low viscosity methyl cellulose 0.3 Attapulgite clay 7.7

These components are blended and micropulzerized until the particles of uracil have been reduced to about 10' microns in diameters, then reblended.

A similar high strength composition can also be made with 5-bromo-6-methyl-3-m-tolyluracil, 5 brorno 6 methyl-3-p-tolyluracil, or 5-bromo-6-methyl-3-(a,a,a-trifluoro-m-tolyl)uracil.

These formulations give excellent weed control when applied pro-emergence or post-emergence at rates of 4 37 pounds per acre to crabgrass, wild oats, wild mustard, volunteer alfalfa, foxtail and lambs quarters.

GRANULES Example 62 Percent 3-sec.-butyl-5-brorno-6-methyluracil, Na salt 25 Granular 8-15 mesh attapulgite clay 75 A granular composition is prepared by dissolving the active ingredient in water and spraying this solution on the attapulgite granules while they are tumbled. The resulting granules are then dried.

The granules are applied by hand for spot treatment of undesirable bunch grasses growing in agricultural areas. An application of 20 to 30 pounds of active ingredient per acre gives good control of Dallis and Vasey grass.

Example 63 Percent 3-cyclohexyl-S-bromo-6-methyluracil 40 Anhydrous sodium sulfate Non-swelling sub-bentonite clay 50 These components are blended and micropulverized then moistened with water and granulated. The granules are then dried and screened.

These granules are applied by hand or by special spreaders at 10 to 25 pounds of active ingredient per acre. They control peppergrass, chickweed, crabgrass, pigweed, smart- Weed, barnyard grass, goose grass, and quack grass on industrial sites, along boundary fences and railroad rightsiof-way, in parking areas, along roadsides, and under billboards.

Example 64 Percent 3-isopropyl-5-chloro-G-methyluracil, Na salt 25 Granular 8-15 mesh vermiculite 75 The granules are prepared by dissolving the active ingredient in water, spraying the solution on tumbling vermiculite granules, and then drying This formulation is used as a spot treatment for areas infested with Russian knapweed, bindweed, and deeprooted perennial weeds. It is applied at 3 pounds per 1000 square feet with a specially adapted spreader.

Example 65 Percent 3-isopropyl-5-bromo-6-methyluracil 40 Anhydrous sodium sulfate 10' Non-swelling Ca, Mg bentonite 49 Alkyl naphthalene sulfonate, Na salt 1 These components are formulated as 4 to 8 mesh granules by blending and grinding the components, then moistgranulating them, followed by drying and screening.

The granules are broadcast at a level of 10 pounds of These ingredients are mixed in a ribbon blender until homogeneous and then charged to a pug mill, where suflicient water is blended in to fornra thick paste. The paste is discharged from the pug mill in the form of extrusions which are dried and broken by a rotary crusher into irregular granules.

3-isopropyl-S-bromo-6methyluracil is also prepared as a granule in this manner.

Example 67 The procedure of Example 66 is used with the following ingredients to give granules of high density.

Percent 3-isopropyl-S-chloro-6-butyluracil 12 Sand (20-30 mesh) 81 Sodium silicate (28% SiO ratio SiO /Na O=3.25) 7 Example 68 fast release) Percent 3-arnyl-5-chloro-6-methyluracil, sodium salt 20 1020 mesh granular, expanded vermiculite The active ingredient is dissolved in water, and the solution is then sprayed on the vermiculite while it is tumbled in a blender. The product is then dried.

Example 69 This product is prepared in the same manner as in Example 68, using the following ingredients:

These granules are prepared by dissolving the active ingredient in water and spraying it on the vermiculite while keeping the vermiculite in motion to assure good distribution, and then drying the product.

Other active materials suitable for the preparation of this type of granule are:

3-benzyl-5-chloro-6-methyluracil, potassium salt 3-tert.-butyl-5bromo-6-methyluracil, sodium salt 3-(l-ethylpropyl)-5-chloro-6-methyluracil, potassium salt 3-norbornyl-5-methoxy-6-methyluracil, sodium salt 3-butyl-5-bromo-6-methyluracil, 1/2 calcium salt Example 71 The granular compositions of Examples 66, 67, 68, 69 and 70 are applied by hand or by specially built spreaders. At concentrations of 25 pounds of active ingredient per acre, they control broadleaf and grass weeds in lumber yards, along railroad rights-of-way, in fire lanes and around billboards, and in parking areas and roadsides.

They can be applied as soil treatments, at 20 pounds of active ingredient per acre, for the control of such woody plants as privet, elm, ash, oak, maple, and Willow. This concentration also gives control of germinating annual Weeds and established perennial'weeds such as quack grass and plantain.

Example 72 Percent 3-tert.-butyl-5-chloro6-methyluracil 3.3 3-phenyl-1,1-dimethylurea 6.7 California Ca, Mg sub-bentonite 75.0 Anhydrous sodium sulfate 15.0

This composition is blended, micropulverized, pug

Example 73 Percent 3 cyclohexyl-S-bromo-6-methyluracil 15 2-chloro-4,6-bis(ethylamino)-s-triazine 15 Sodium lignin sulfonate 10 Swollen corn starch 4 Water 56 The active components, the sodium lignin sulfonate,1and sufficient water to make a 50% slurry are first ball-milled 39 until the particles are less than microns in size. The starch is then swelled with heat in the balance of the water and mixed with the dispersion.

Four parts of this dispersion are then sprayed on 26 parts of tumbling granular attaclay and dried to give granules containing 4% active ingredient.

A spring application of 2 pounds (active) per acre of these 4% granules gives excellent pie-emergence control of such annual weeds as wild carrot, crabgrass, goldenrod, lambs-quarters, ragweed, and dog-fennel in asparagus.

Example 74 Percent 3-sec.-butyl-5-bromo-6-methyluracil 3.75 2,3,6-trichlorobenzoic acid, Na salt 11.25 Attaclay, -30 mesh 85.00

The trichlorobenzoic acid salt is dissolved in water. Finely ground uracil is then suspended in this solution, with vigorous agitation, The mix is sprayed on tumbling attaclay and dried.

These granules are applied at the rate of pounds (active) per acre for the control of field bindweed, crabgrass, ragweed, bluegrass, and pigweed growing in lumber yards.

As little as 10 pounds (active) per acre gives control of such annual grasses as crabgrass and foxtail and controls a heavy infestation of Virginia creeper.

Example 75 Percent 3-is0pr0pyl-5-chloro-6-methyluracil 2.0 Sodium chlorate 38.4 Sodium borate 59.6

A mixture of the crystalline chlorate and borate is placed in a blender. Finely ground uracil is slurried in water and sprayed on the chlorate-borate mixture while it is blended.

This formulation is effective against grass and broadleaf weed infestations, and can be easily applied on railroad rights-of-way. An application of 400 pounds per acre of these granules gives outstanding control of little bluestem, broomsedge, foxtail, crabgrass, ragweed, pigweed, henbit, and knotweed.

Example 76 Percent 3-sec.-butyl-S-chloro-6-methyluracil 5.0 3-sec.-butyl-5,6-trimethyleneuracil 10.0 Na SO anhydrous 10.0 Sodium lignin sulfonate 10.0 Mississippi sub-bentonite 32.5 Kaolinclay 32.5

These ingredients are blended and micropulverized until substantially all particles are less than 50 microns in size. The blend is then pug-milled with 15-20% water, moist-granulated, dried, and screened to 8-30 mesh.

When this formulation is applied at the rate of 6 pounds (active) per acre, excellent control of a wide variety of annual weeds is obtained.

Example 77 Percent 3-isopropyl-5-nitro-6-methyluracil 1 Granular 15-30 mesh attapulgite 99 The uracil is dissolved in acetone and sprayed as a fine fog on tumbling granular attaclay. The solvent is then evaporated.

This granular formulation is applied at the rate of 120 pounds per acre. Excellent pre-emergence control of germinating weeds is obtained in a newly-planted field of peanuts. Carpetweed, foxtail, crabgrass, and lambsquarters are controlled with no visible injury to the crop. 7

40 Example 78 Percent 3,5-di-(sec.-butyl)-6-methyluracil 25 Alkyl naphthalene sulfonic acid, sodium salt 1 Lignin sulfonic acid, sodium salt 1 Attapulgite clay 73 These ingredients are blended and then charged to a grinding mill where the are ground and moist granulated. The resulting granules are then dried and screened.

The following uracils can be formulated in the same fashion:

These compositions control cheat and wild oats growing along roadsides when applied pre-emergence at 12- 15 pounds (active) per acre.

PELLETS Example 79 Percent 3-isopropyl-5-chloro-6-methyluraci l 25 Anhydrous sodium sulfate 10 Sodium lignin sulfonate 10 Ca, Mg. bentonite 55 These components are blended and micropulverized, then moistened with 18-20% water and extruded through die holes. The extusions are cut into pellets and then dried.

These pellets are useful for weed control along highway guard rails, around bridges, cyclone fences, and highway signs. They are applied by hand, at 10 to 25 pounds of active ingredient per acre. Excellent control of such woody plants as oak, maple, sweet gum, and willow is obtained.

Example 80 Percent 3-phenyl-5-bromo-6-methyl-2-thiouracil 25 Allkyl naphthalene sulfonic acid, Na salt 1 Anhydrous sodium sulfate 10 Non-swelling montmorillonoid type clay (Pikes Peak clay) 64 These components are blended and micropulverized, then wetted with 18-25% water and extruded through a die. The extrusions are cut into /8 inch pellets and then dried.

This formulation is used for dry application to the soil for control of undesirable woody plants in fence rows and utility rights-of-way. A basal application of one tablespoonful on the ground at the base of each brush cluster gives excellent control of birch, box elder, wild cherry, privet, willow, dogwood, oak, sweetgum, and poplar. 

19. A METHOD FOR THE CONTROL OF UNDERSIRABLE VEGETATION COMPRISING APPLYING TO A LOCUS TOBE PROTECTED IN AN AMOUNT SUFFICIENT TOEXERT HERBICIDAL ACTION A COMPOUND SELECTED FROM THE GROUP CONSISTING OF: (A) COMPOUNDS OF THE FORMULA 